USO DE UM CATALISADOR DE POLIMERIZAÇÃO DE BIFENILFENOL EM FASE GASOSA SUPORTADO PARA PRODUZIR TANTO (I) QUANTO (II) UM POLÍMERO ATRAVÉS DE UM PROCESSO DE POLIMERIZAÇÃO EM FASE GASOSA E MÉTODO DE POLIMERIZAÇÃO EM FASE GASOSA PARA PRODUZIR TANTO UM POLÍMERO (A) QUE TEM UM PESO MOLECULAR (MW) EM UMA FAIXA DE 150.000 DALTONS A 1.200.000 DALTONS, QUANTO UM POLÍMERO (B) QUE TEM UM MW MENOR QUE 500.000 DALTONS

Abstract

USE OF A GAS-PHASE BIPHENYLPHENOL POLYMERIZATION CATALYST, POLYMERIZATION CATALYST SYSTEM, POLYMERIZATION METHOD, AND POLYETHYLENE COMPOSITION. The embodiments are directed to the use of a supported gas-phase biphenylphenol polymerization catalyst to produce a polymer through a gas-phase polymerization process, wherein the supported gas-phase biphenylphenol polymerization catalyst is produced from a gas-phase biphenylphenol polymerization pre-catalyst of Formula I.

Description

[001] Embodiments of the present disclosure are directed to gas-phase biphenylphenol polymerization catalysts, more specifically, gas-phase biphenylphenol polymerization catalysts that can be used to produce a polymer via a gas-phase polymerization process. BACKGROUND

[002] Polymers can be used for a range of products including films, fibers, nonwoven and / or woven fabrics, extruded and / or molded articles, among others. Polymers can be made by reacting one or more types of monomers in a polymerization reaction in the presence of a polymerization catalyst. SUMMARY

[003] The present disclosure provides several modalities which include:

[004] A use of a supported gas-phase biphenylphenol polymerization catalyst to produce a polymer via a gas-phase polymerization process, wherein the gas-phase biphenylphenol polymerization catalyst is produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I: Petition 870260054527, dated 05 / 06 / 2026, page 12 / 100 2 / 41 (Formula I) wherein each of R5, R7, R8 and R10 is independently a C1 to C20 alkyl, aryl, aralkyl, a halogen or a hydrogen; wherein each of R4 and R11 is independently a halogen or a hydrogen; wherein each of R2 and R13 is independently a C1 to C20 alkyl, aryl or aralkyl, or a hydrogen; wherein each of R15 and R16 is independently a 2,7-disubstituted carbazol-9-yl or a 3,6-disubstituted carbazol-9-yl; wherein L is a linear C3 or C4 alkylene that forms a 3-carbon bridge or a 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded; wherein each of R1, R3, R12 and R14 is independently a C1-C5 alkyl, a halogen or a hydrogen; wherein each of R6 and R9 is a hydrogen or a C1-C1 alkyl group;wherein each X is independently a halogen, a hydrogen, a C1-C20 alkyl, a C7-C20 aralkyl, a C6-C12 aryl substituted by C1-C1 alkyl or a C1-C1 alkyl substituted by benzyl, -CH2Si(Rc)3, wherein Rc is a C1-C12 hydrocarbon; and wherein M is zirconium (Zr) or hafnium (Hf). DETAILED DESCRIPTION

[005] A supported gas-phase biphenylphenol polymerization catalyst that can be used to produce a polymer via a gas-phase polymerization process is produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I: Petition 870260054527, dated 05 / 06 / 2026, page 13 / 100 3 / 41 R5R6R9R10 (Formula I) wherein each of R5, R7, R8 and R10 is independently a C1 to C20 alkyl, aryl, aralkyl, a halogen or a hydrogen; wherein each of R4 and R11 is independently a halogen or a hydrogen; wherein each of R2 and R13 is independently a C1 to C20 alkyl, aryl or aralkyl, or a hydrogen; wherein each of R15 and R16 is independently a 2,7-disubstituted carbazol-9-yl or a 3,6-disubstituted carbazol-9-yl; wherein L is a linear C3 or C4 alkylene that forms a 3-carbon bridge or a 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded; in each of R1, R3, R12 and R14 is independently a C1-C5 alkyl, a halogen or a hydrogen; wherein each of R6 and R9 is a hydrogen or a C1-C1 alkyl;wherein each X is independently a halogen, a hydrogen, a C1-C20 alkyl, a C7-C20 aralkyl, a C6-C12 aryl substituted by C1-C6 alkyl or a C1-C6 alkyl substituted by benzyl, -CH2Si(Rc)3, wherein Rc is a C1-C12 hydrocarbon; and wherein M is Zr or Hf.

[006] The gas-phase biphenylphenol polymerization precatalyst represented by Formula I (i.e., the gas-phase biphenylphenol polymerization precatalyst), as described herein, can be used to produce gas-phase biphenylphenol polymerization catalysts. For example, the gas-phase biphenylphenol polymerization precatalyst represented by Formula I can be contacted, under activation conditions, with an activator in order to activate the gas-phase biphenylphenol polymerization precatalyst represented by Formula I, thus producing the gas-phase biphenylphenol polymerization catalyst. Petition 870260054527, dated 05 / 06 / 2026, page 14 / 100 4 / 41 gaseous.

[007] As mentioned, each of R5, R7, R8 and R10, as shown in Formula I, can independently be a C1 to C20 alkyl, aryl, aralkyl, a halogen or a hydrogen. One or more embodiments state that each of R5, R7, R8 and R10 is a halogen, such as fluorine. One or more embodiments state that each of R5, R7, R8 and R10 is a halogen, such as fluorine. One or more embodiments state that each of R5 and R10 is a halogen, such as fluorine. One or more embodiments state that each of R5 and R10 is a silyl substituted with alkyl or aryl. One or more embodiments state that each of R5 and R10 is a silyl substituted with dialkyl or trialkyl. One or more embodiments state that each of R5 and R10 is an octyldimethylsilyl.

[008] One or more embodiments state that each of R1, R3, R12 and R14 is independently a C1-C8 alkyl, a halogen or a hydrogen. One or more embodiments state that each of R1, R3, R12 and R14 is a hydrogen. One or more embodiments state that each of R1, R3, R12 and R14 is a hydrogen.

[009] One or more embodiments state that at least one of R7 and R8 is a hydrogen. One or more embodiments state that each of R7 and R8 is a hydrogen. One or more embodiments state that at least one of R7 and R8 is a C1 alkyl, for example, methyl. One or more embodiments state that each of R7 and R8 is a methyl.

[0010] One or more embodiments state that each of R6 and R9 is a hydrogen or C1-C8 alkyl. One or more embodiments state that each of R6 and R9 is a hydrogen.

[0011] As used herein, an alkyl includes linear, branched, and cyclic paraffin radicals that are deficient in a hydrogen. Thus, for example, a CH3 (methyl) group and a CH3CH2 (ethyl) group are examples of alkyls. Petition 870260054527, dated 05 / 06 / 2026, page 15 / 100 5 / 41

[0012] As used in this document, aryl includes phenyl, naphthyl, pyridyl, and other radicals whose molecules have the characteristic ring structure of benzene, naphthylene, phenanthrene, anthracene, etc. It is understood that an aryl can be a C6 to C20 aryl. For example, an aromatic structure C6H5- is a phenyl, an aromatic structure C6H4- is a phenylene. As used herein, an aralkyl, which may also be called an arylalkyl, is an alkyl that has an aryl group hanging from it. It is understood that an aralkyl can be a C7 to C20 aralkyl. An alkylaryl is an aryl having one or more alkyl groups hanging from it. As used herein, a hydrocarbyl includes aliphatic, cyclic, olefinic, acetylenic, and aromatic radicals (i.e., hydrocarbon radicals) comprising hydrogen and carbon that are deficient in one hydrogen.

[0013] As mentioned, each of R4 and R11, as shown in Formula I, can independently be a hydrogen or a halogen, such as fluorine. For example, one or more embodiments state that each of R4 and R11 is a hydrogen.

[0014] As mentioned, each of R2 and R13, as shown in Formula I, can independently be a C1 to C20 alkyl, aryl or aralkyl, or a hydrogen. One or more embodiments state that each of R2 and R13 is a C3-C4 alkyl such as n-butyl, t-butyl, or 2-methylpentyl. One or more embodiments state that each of R2 and R13 is a 1,1,3,3-tetramethylbutyl. One or more embodiments state that each of R2 and R13 is a C1 alkyl, that is, a methyl.

[0015] As mentioned, each of R15 and R16, as shown in Formula I, can be a 2,7-disubstituted carbazol-9-yl or a 3,6-disubstituted carbazol-9-yl. For example, one or more embodiments state that each of R15 and R16 is a 2,7-disubstituted carbazol-9-yl selected from a group consisting of a 2,7-di-t-butylcarbazol-9-yl, a 2,7-diethylcarbazol-9-yl, a 2,7 Petition 870260054527, dated 05 / 06 / 2026, page 16 / 100 6 / 41 dimethylcarbazol-9-yl and a 2,7-bis(di-isopropyl(n-octyl)silyl)-carbazol-9-yl. For example, one or more embodiments state that each of R15 and R16 is a 3,6-disubstituted carbazol-9-yl selected from a group consisting of a 3,6-di-t-butylcarbazol-9-yl, a 3,6-diethylcarbazol-9-yl, a 3,6-dimethylcarbazol-9-yl and a 3,6-bis(di-isopropyl(n-octyl)silyl)-carbazol-9-yl.

[0016] As mentioned, L, as shown in Formula I, can be a C3 or C4 alkylene that forms a 3-carbon bridge or a 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded. For example, in one or more embodiments, L can be a saturated C3C4 alkyl that forms a 3-carbon or 4-carbon bridge between the two oxygen atoms to which L is bonded. One or more embodiments state that L is a saturated C3 alkyl that forms a bridge between the two oxygen atoms to which L is bonded. The term saturated means a lack of carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double or triple bonds. One or more embodiments state that L is a saturated C4 alkyl that forms a bridge between the two oxygen atoms to which L is bonded.

[0017] As mentioned, each X, as shown in Formula I, can independently be a halogen, a hydrogen, a C1-C20 alkyl, a C7-C20 aralkyl, a C1-C6 alkyl-substituted C6-C12 aryl, or a C1-C6 alkyl-substituted benzyl, -CH2Si(RC)3, where RC is a C1-C12 hydrocarbon. For example, one or more embodiments state that each X is a C1-C12 alkyl.

[0018] As mentioned, M, as shown in Formula I, is a heteroatom, just like a metal atom. In some embodiments, M can be selected from a group consisting of Zr and Hf. One or more embodiments state that M is zirconium. One or more embodiments state that M is hafnium.

[0019] Each of the R groups (R1-R16) and the X groups of Formula I, as described here, Petition 870260054527, dated 05 / 06 / 2026, p. 17 / 100 7 / 41 can be independently substituted or unsubstituted. For example, in some embodiments, each of the X's in Formula I can independently be a C6-C12 aryl substituted by a C1-C6 alkyl or a C1-C6 benzyl substituted by an alkyl. As used herein, substituted indicates that the group accompanying that term has at least one moiety in place of one or more hydrogens in any position, moieties being selected from such groups as halogen radicals, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxyl groups, phenyl groups, naphthyl groups, C1a-C20 alkyl groups, C2a-C10 alkenyl groups, and combinations thereof.Being disubstituted refers to the presence of two or more substituent groups at any position, with the portions being selected from these groups, such as halogen radicals, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxyl groups, phenyl groups, naphthyl groups, C1 to C20 alkyl groups, C2 to C10 alkenyl groups, and combinations thereof.

[0020] The metallocene olefin polymerization catalyst and a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst in the present invention can be produced using reagents mentioned herein. The metallocene olefin polymerization catalyst and a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst in the present invention can be produced by various processes, for example, with conventional solvents, reaction conditions, reaction times and isolation procedures, used to produce known catalysts, such as known metallocene olefin polymerization catalysts.

[0021] One or more embodiments provide a polymerization catalyst, especially a biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I. The gas-phase biphenylphenol polymerization catalyst can be produced Petition 870260054527, dated 05 / 06 / 2026, page 18 / 100 8 / 41 bringing gas-phase biphenylphenol polymerization precatalysts into contact, under activation conditions, with an activator to provide the gas-phase biphenylphenol polymerization catalyst, for example, an activated gas-phase biphenylphenol polymerization precatalyst. The activation conditions are well known in the art.

[0022] As used herein, activator refers to any compound or combination of compounds, supported or unsupported, that can activate a complex or a catalyst component, such as by creating a cationic species of the catalyst component. For example, this may include the abstraction of at least one leaving group, for example, the X group described in the present invention, from the metal center of the complex / catalyst component, for example, the metal complex of Formula I. As used herein, leaving group refers to one or more chemical moieties attached to a metal atom that can be abstracted by an activator, thus producing an active species for olefin polymerization.

[0023] The activator may include a Lewis acid or a non-coordinating ionic activator or ionizing activator, or any other compound that includes Lewis bases, aluminum alkyls and / or conventional type cocatalysts.In addition to the methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) mentioned above, illustrative activators may include, but are not limited to, aluminoxane or modified aluminoxane and / or ionizing compounds, neutral or ionic, such as Dimethylaniline tetrakis(pentafluorophenyl)borate, Triphenylcarbenium tetrakis(pentafluorophenyl)borate, Dimethylaniline tetrakis(3,5-(CF3)2phenyl)borate, Triphenylcarbenium tetrakis(3,5-(CF3)2phenyl)borate, Dimethylaniline tetrakis(perfluoronaphthyl)borate, Triphenylcarbenium tetrakis(perfluoronaphthyl)borate, Dimethylaniline tetrakis(pentafluorophenyl)aluminate, Triphenylcarbenium tetrakis(pentafluorophenyl)aluminate, Dimethylaniline tetrakis(perfluoronaphthyl)aluminate, Triphenylcarbenium tetrakis(perfluoronaphthyl)aluminate, a tris(perfluorophenyl)boron, a. Petition 870260054527, dated 05 / 06 / 2026, page 19 / 100 9 / 41 tris(perfluoronaphthyl)boron, tris(perfluorophenyl)aluminum, a tris(perfluoronaphthyl)aluminum or any combination thereof.

[0024] Aluminoxanes can be described as oligomeric aluminum compounds having -Al(R)-O- subunits, where R is an alkyl group. Examples of aluminoxanes include, but are not limited to, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, isobutylaluminoxane, or a combination thereof. Aluminoxanes can be produced by hydrolysis of the respective trialkylaluminum compound. MMAO can be produced by hydrolysis of trimethylaluminum and a higher trialkylaluminum, such as triisobutylaluminum. There are a variety of known methods for preparing aluminoxane and modified aluminoxanes. Aluminoxane may include a modified methylaluminoxane (MMAO) type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane type 3A, discussed in US Patent No. 5,041,584). A source of MAO can be a solution that has from about 1%, by weight, to about 50%, by weight, of MAO, for example.Commercially available MAO solutions may include 10% by weight and 30% by weight MAO solutions, available from Albemarle Corporation, Baton Rouge, LA, USA.

[0025] One or more organoaluminum compounds, such as one or more alkylaluminum compounds, may be used in conjunction with aluminoxanes. Examples of alkylaluminum compounds include, but are not limited to, diethylaluminum ethoxide, diethylaluminum chloride, diisobutylaluminum hydride, and combinations thereof. Examples of other alkylaluminum compounds, for example, trialkylaluminum compounds, include, but are not limited to, trimethylaluminum, triethylaluminum (TEAL), triisobutylaluminum (TiBAl), tri-n-hexylaluminum, tri-n-octylaluminum, tripropylaluminum, tributylaluminum, and combinations thereof.

[0026] The metallocene olefin polymerization catalyst can be any metallocene olefin polymerization catalyst. In one or more embodiments, the Petition 870260054527, dated 05 / 06 / 2026, p. 20 / 100 10 / 41 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-propylcyclopentadienyl)2MX2, (n-butylcyclopentadienyl)2MX2, (1-methyl,3-n-butylcyclopentadienyl)2MX2, (cyclopentadienyl)(1,3-dimethyltetrahydroindenyl)MX2, (methylcyclopentadienyl)(1,3-dimethyltetrahydroindenyl)MX2, (cyclopentadienyl)(1,5-dimethylindenyl)MX2, (methylcyclopentadienyl)(1,5-dimethylindenyl)MX2, (cyclopentadienyl)(1,4-dimethylindenyl)MX2, (methylcyclopentadienyl)(1,4-dimethylindenyl)MX2, (cyclopentadienyl)(1,7-dimethylindenyl)MX2, (methylcyclopentadienyl)(1,7-dimethylindenyl)MX2 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 alkyls or alkenyls.

[0027] A gas-phase polymerization catalyst system comprising a metallocene olefin polymerization catalyst; and a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst, can be used to produce a polymer. For example, the gas-phase polymerization catalyst system and an olefin can be brought into contact under polymerization conditions in a gas-phase polymerization reactor to produce a polymer, for example, a polyolefin polymer.

[0028] As used in this document, a polymer has two or more of the same or different polymer units derived from one or more different monomers, for example, homopolymers, copolymers, terpolymers, etc. A homopolymer is a polymer that has polymer units that are the same. A copolymer is a polymer that has two or more polymer units that are different from each other. A terpolymer is a polymer that has three units of Petition 870260054527, dated 05 / 06 / 2026, page 21 / 100 11 / 41 polymers that are different from each other. Different in reference to polymer units indicates that the polymer units differ from each other by at least one atom or are isomerically different. Consequently, the definition of copolymer, as used herein, includes terpolymers and the like. As used in this document, a polymerization process is a process that is used to make a polymer.

[0029] The embodiments establish that the polymer may be a polyolefin polymer. As used herein, an olefin, which may be called an alkene, refers to a linear, branched, or cyclic compound that includes carbon and hydrogen and that has at least one double bond. As used herein, when a polymer or copolymer is referred to as comprising, for example, being produced from, an olefin, the olefin present in that polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 1% by weight to 99% by weight, it is understood that the polymer unit in the copolymer is derived from ethylene in the polymerization reaction and the derived units are present in 1% by weight to 99% by weight, based on the total weight of the polymer. A higher α-olefin refers to an α-olefin having 3 or more carbon atoms.

[0030] Polyolefins include polymers made from olefin monomers, such as ethylene, i.e., polyethylene, and linear or branched higher alpha-olefin monomers containing from 3 to 20 carbon atoms. Examples of higher alpha-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, which have at least 50% ethylene by weight, including copolymers of ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene, among others. Other olefins that can be used include ethylenically unsaturated monomers, diolefins with 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cyclic olefins, for example. Examples Petition 870260054527, dated 05 / 06 / 2026, page 22 / 100 12 / 41 of the monomers may include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl-substituted styrene, ethylidenonorbornene, dicyclopentadiene, and cyclopentene. In several embodiments, an ethylene copolymer can be produced, in which ethylene, a comonomer having at least one alpha-olefin with 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, and most preferably 4 to 8 carbon atoms, is polymerized, for example, in a gas-phase polymerization process. In another embodiment, ethylene and / or propylene can be polymerized with at least two different comonomers, optionally one of which may be a diene, to make a terpolymer.

[0031] One or more embodiments state that the polymer may include from 1 to 100% by weight of ethylene-derived units based on the total weight of the polymer. All individual values ​​and subranges from 1 to 100% by weight are included; for example, the polymer may include from a lower limit of 1, 5, 10 or 50% by weight of ethylene-derived units to an upper limit of 100, 95, 90, 85 or 75% by weight of ethylene-derived units based on the total weight of the polymer.

[0032] The gas-phase polymerization catalyst system including a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I can help deliver polymers through a polymerization process in a single gas-phase reactor. In one or more embodiments, the resulting polymers may have at least one high molecular weight polyethylene component and one 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 and low molecular weight polyethylene components are Petition 870260054527, dated 05 / 06 / 2026, page 23 / 100 13 / 41 formed together in a single gas-phase reactor through a polymerization process employing a gas-phase polymerization catalyst system. Having a high molecular weight polyethylene component and a low molecular weight polyethylene component is desirable in some applications.

[0033] Surprisingly, the gas-phase polymerization catalyst system including a biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I of the disclosure can produce polymers including high molecular weight polyethylene components that have a lower molecular weight compared to high molecular weight components in polymers formed with other (non-inventive) polymerization catalysts under similar polymerization conditions, as detailed in the present invention. High molecular weight polyethylene components with a lower molecular weight than other high molecular weight polyethylene components are desirable in some applications.

[0034] Embodiments specify that the polymer may have a Mn (number average molecular weight) of 8,000 to 250,000. All individual values ​​and subranges from 8,000 pm to 250,000 pm are included; for example, the polymer may have an Mn from a lower limit of 8,000; 10,000; or 12,000; up to an upper limit of 250,000; 150,000; 100,000; 40,000; or 35,000. In some embodiments, the Mn may be in a range of 12,702 to 245,010.

[0035] Embodiments specify that the polymer may have a weight-average molecular weight (Mw) of 50,000 to 1,200,000 under conditions B and / or a molecular weight less than 500,000 daltons under conditions K. All individual values ​​and subranges from 50,000 pm to 1,200,000 pm are included; for example, the polymer may have an Mw from a lower limit of 50,000; 100,000; or 200,000; up to an upper limit of 1,200,000; 1,100,000; 1,000,000; 800,000 or 600,000 under conditions B. Some embodiments specify that the polymer may have a weight-average molecular weight Petition 870260054527, dated 05 / 06 / 2026, p. 24 / 100 14 / 41 average) from 50,000 to 800,000 under B conditions and / or a molecular weight less than 500,000 daltons under K conditions. All individual values ​​and subranges from 50,000 pm to 800,000 pm are included; for example, the polymer may have a Mw from a lower limit of 50,000; 100,000; or 200,000; to an upper limit of 800,000; or 600,000 under B conditions. In some examples, the polymer may have an Mw of 50,000 to 500,000 under K conditions or of 100,000 to 500,000 under K conditions.

[0036] The embodiments establish that the polymer may have an Mz (average molecular weight z) from 200,000 to 10,000,000. All individual values ​​and subranges from 200,000 pm to 10,000,000 pm are included; for example, the polymer may have an Mz from a lower limit of 200,000; 700,000; or 900,000; up to an upper limit of 10,000,000; 5,000,000; or 3,000,000.

[0037] Modalities establish that the polymer may have a ratio between Mz and Mw in the range of 2.00 to 20.00. All individual values ​​and subranges from 2.00 pm to 20.00 pm are included; for example, the polymer may have a ratio between Mz and Mw from a lower limit of 2.00; 3.00; or R$ 4.00 up to an upper limit of R$ 20.00, R$ 15.00 or R$ 10.00.

[0038] In some embodiments, the polymer may have a Mw to Mn ratio value that is greater than 2.00, greater than 3.00, greater than 4.00, or greater than 5.00. For example, embodiments specify that the polymer may have an Mw to Mn ratio in the range of 5.00 to 75.00. All individual values ​​and subranges from 5.00 pm to 75.00 pm are included; for example, the polymer may have an Mw to Mn ratio from a lower limit of 5.00, 6.00, or 7.00 to an upper limit of 75.00, 60.00, or 50.00.

[0039] Modalities establish that the polymer may have a ratio between Mz and Mw that is less than a ratio between Mw and Mn of the polymer.

[0040] The embodiments establish that the polymer may have a melt index (I21) as measured by ASTM D1238 (at 190 °C, 21 kg load) in the range of 0.001 dg / 1 min to 1.000 dg / 1 min. All individual values ​​and subranges from 0.001 dg / 1 min to 1.000 dg / 1 min are included. Petition 870260054527, dated 05 / 06 / 2026, p. 25 / 100 15 / 41

[0041] The embodiments establish that the polymer produced using a gas-phase polymerization reactor may have a melting temperature (Tm) of 110 to 135 degrees Celsius (°C). All individual values ​​and subranges from 118 to 135 °C are included; for example, the polymer may have a Tm from a lower limit of 110, 113, 118, 119 or 120 to an upper limit of 135, 133, 132, 130 or 128 °C.

[0042] The embodiments establish that the polymer may have a density of 0.890 g / cm3 to 0.970 g / cm3. All individual values ​​and subranges from 0.890 to 0.970 g / cm3 are included; for example, the polymer may have a density from a lower limit of 0.890, 0.900, 0.910, 0.920 or 0.940 g / cm3 to an upper limit of 0.970, 0.960 or 0.950 g / cm3. Density may be determined in accordance with ASTM D-79213, 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, for example, in liquid 2-propanol). Report the results in units of grams per cubic centimeter (g / cm3).

[0043] Gel permeation chromatography (GPC) test method: Weight-average molecular weight test method: determine the Mw, number-average molecular weight (Mn), and Mw / Mn using chromatograms obtained on a high-temperature gel permeation chromatography instrument (HTGPC, Polymer Laboratories). The HTGPC is equipped with transfer lines, a differential refractive index (DRI) detector, and three Polymer Laboratories PLgel 10 pm MixedB columns, all contained in an oven maintained at 160 °C. The method uses a BHT-treated TCB solvent at a nominal flow rate of 1.0 milliliter per minute (mL / min) and a nominal injection volume of 300 microliters (µL). Prepare the solvent by dissolving 6 grams of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent-grade 1,2,4-trichlorobenzene (TCB) and filtering the resulting solution through a 0.1 micrometer (µm) Teflon filter to give the solvent.Degas the solvent using an in-line degasser before it enters the... Petition 870260054527, dated 05 / 06 / 2026, page 26 / 100 16 / 41 HTGPC instrument. Calibrate the columns with a series of monodisperse polystyrene (PS) standards. Separately, prepare known concentrations of test polymer dissolved in solvent by heating known quantities of the polymer in known volumes of solvent to 160°C with continuous stirring for 2 hours to give the solutions. (Measure all quantities gravimetrically.) Target solution concentrations, c, of the test polymer range from 0.5 to 2.0 milligrams of polymer per milliliter of solution (mg / mL), with lower concentrations, c, used for higher molecular weight polymers. Before running each sample, purge the DRI detector. Then, increase the flow rate in the instrument to 1.0 mL / min and allow the DRI detector to stabilize for 8 hours before injecting the first sample. Calculate Mwe and M using universal calibration relationships with the column calibrations. Calculate the MW in each elution volume using the following equation: , log(Ky / XpJ cí^+I. ,, log Mx=&log ax+1 ax+1

[0044] where the subscript X means the test sample, the subscript PS means PS standards, aps = 0.67, KPs = 0.000175, and αχ are obtained from published literature. For polyethylenes, ax / Kx = 0.695 / 0.000579. For polypropylenes, ax / Kx = 0.705 / 0.0002288. At each point in the resulting chromatogram, calculate the concentration, c, from a DRI signal subtracted from the reference base, Idri, using the following equation: c = KDRi / Idri / (dn / dc), where KDri is a constant determined by calibrating the DRI, / indicates division, and dn / dc is the refractive index increment for the polymer. For polyethylene, dn / dc = 0.109. Calculate the polymer mass recovery from the ratio of the integrated area of ​​the concentration chromatography chromatogram to the elution volume and the injection mass, which is equal to the predetermined concentration multiplied by the injection circuit volume. Report all molecular weights in grams per mole (g / mol) unless otherwise indicated. Details Petition 870260054527, dated 05 / 06 / 2026, page 27 / 100 17 / 41 additional information regarding methods for determining Mw, Mn, MWD is described in US 2006 / 0173123, pages 24 and 25, paragraphs

[0334] to

[0341] . Plotting dW / dLog(MW) on the geometric y-axis versus Log(MW) on the geometric x-axis provides a GPC chromatogram, where Log(MW) and dW / dLog(MW) are as defined above.

[0045] The polymer can be used for a range of articles, such as films, fibers, nonwoven and / or woven fabrics, extruded and / or molded articles, among others.

[0046] A gas-phase polymerization catalyst system is provided for producing a polymer via a gas-phase polymerization process, wherein the gas-phase polymerization catalyst comprises: a metallocene olefin polymerization catalyst; and the supported gas-phase biphenylphenol polymerization catalyst produced from the gas-phase biphenylphenol polymerization precatalyst of Formula I, as detailed in the present invention.

[0047] The metallocene olefin polymerization catalyst and / or a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I, as well as other components discussed in this document, such as the activator, can be used with a support. A support, which may also be called a carrier, refers to any supporting material, which includes a porous supporting material such as talc, inorganic oxides, and inorganic chlorides.

[0048] The metallocene olefin polymerization catalyst and / or a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I, as well as other components discussed in this document, may be supported on the same support or on separate supports, or one or more of the components may be used in an unsupported form. The use of the support may be carried out by any practice. Petition 870260054527, dated 05 / 06 / 2026, page 28 / 100 18 / 41 used in the technique. One or more embodiments establish that a spray drying process is used. Spray drying processes are well known in the art. The support can be functionalized.

[0049] The support may be a porous support material, for example, talc, an inorganic oxide or an inorganic chloride. Other support materials include resinous support materials, for example, polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinylbenzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

[0050] Support materials include inorganic oxides which include 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 magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Combinations of these support materials may also be used, for example, silica-chromium, silica-alumina, silica-titania, and the like. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymeric microspheres.

[0051] An example of a support is pyrolyzed silica available under the trade name Cabosil™ TS-610 or other TS or TG series supports available from Cabot Corporation. Pyrolyzed silica is typically silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride so that most of the surface hydroxyl groups are capped.

[0052] The support material may have a surface area in the range of about 10 to about 700 m2 / g, a pore volume in the range of about 0.1 to about 4.0 g / cm3 and an average particle size in the range of about 5 to about 500 µm. More preferably, the surface area of ​​the support material is in the range of about 50 to about 500 m2 / g, the pore volume of about 0.5 to about 3.5 g / cm3 and the Petition 870260054527, dated 05 / 06 / 2026, page 29 / 100 19 / 41 average particle size of about 10 to about 200 µm. Most preferably, the surface area of ​​the support material is in the range of about 100 to about 400 m² / g, the pore volume of about 0.8 to about 3.0 g / cm³, and the average particle size is about 5 to about 100 µm. The average pore size of the carrier typically has a pore size in the range of 10 to 1,000 Å, preferably 50 to about 500 Å, and most preferably 75 to about 350 Å.

[0053] The metallocene olefin polymerization catalyst and / or a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I, as well as other components discussed in this document, such as the activator, can be submitted in the form of a flowable paste. Flowable pastes are well known in the art. The flowable paste may include the metallocene olefin polymerization catalyst and / or a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I, an activator, and a support, for example.

[0054] A molar ratio between metal in the activator and metal in a metallocene olefin polymerization catalyst or the gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I in the flow paste may be 20,000:1 to 0.5:1, 20,000:1 to 2,000:1, 20,000:1 to 5,000:1, 20,000:1 to 10,000:1, 1,000:1 to 0.5:1, 300:1 to 1:1, or 150:1 to 1:1. One or more diluents, for example, fluids, may be used to facilitate the combination of any two or more components in the flow paste. For example, the metallocene olefin polymerization catalyst and / or a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I and the activator can be combined together in the presence of toluene or another mixture of Petition 870260054527, dated 05 / 06 / 2026, page 30 / 100 20 / 41 hydrocarbons or non-reactive hydrocarbons. In addition to toluene, other suitable diluents may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. The dry or toluene-mixed support may then be added to the mixture, or the metal-ligand complex / activator may be added to the support. The flowable paste may be fed into the reactor for the polymerization process and / or the flowable paste may be dried, for example, spray-dried, before being fed into the reactor for the polymerization process.

[0055] As mentioned, the polymerization process can be a gas-phase polymerization process using a gas-phase polymerization reactor. The polymerization process can use known equipment and reaction conditions, for example, known polymerization conditions. As an example, polymerization temperatures can range from about 0°C to about 300°C at atmospheric, subatmospheric, or superatmospheric pressures. The embodiments provide a method for producing a polyolefin polymer, wherein the method comprises: contacting, under polymerization conditions, an olefin with the gas-phase polymerization catalyst system, as described herein, to polymerize the olefin, thereby producing a polyolefin polymer.

[0056] One or more embodiments establish that the polymers can be formed through a gas-phase polymerization system, at superatmospheric pressures in the range of 0.07 to 68.9 bar, 3.45 to 27.6 bar or 6.89 to 24.1 bar and a temperature in the range of 30 °C to 130 °C, 65 °C to 110 °C, 75 °C to 120 °C or 80 °C to 120 °C. Fluidized and / or stirred bed gas-phase polymerization systems may be used.

[0057] Generally, a conventional gas-phase fluidized bed polymerization process can be carried out by continuously passing a stream containing one or more olefin monomers through a fluidized bed reactor under Petition 870260054527, dated 05 / 06 / 2026, page 31 / 100 21 / 41 reaction conditions and in the presence of a catalytic composition, for example, a composition that includes the gas-phase polymerization catalyst system (a metallocene olefin polymerization catalyst and a gas-phase biphenylphenol polymerization catalyst produced from a gas-phase biphenylphenol polymerization pre-catalyst of Formula I) and the activator, at a rate sufficient to maintain a bed of solid particles in a suspended state. A stream comprising unreacted monomer can be continuously withdrawn from the reactor, compressed, cooled, optionally partially or totally condensed, and recycled back to the reactor. The product, i.e., polymer, can be withdrawn from the reactor and replacement monomer can be added to the recycle stream. Gases inert to the catalyst and reactant composition may also be present in the gas stream.The polymerization system may include a single reactor or two or more reactors in series, for example.

[0058] Feed streams for the polymerization process may include olefin monomer, non-olefinic gas such as nitrogen and / or hydrogen, and may additionally include one or more non-reactive alkanes that may be condensable in the polymerization process and used to remove the heat of reaction. Illustrative non-reactive alkanes include, but are not limited to, propane, butane, isobutane, pentane, isopentane, hexane, isomers thereof and derivatives thereof. Feeds may enter the reactor at a single location or at several different locations.

[0059] For the polymerization process, the polymerization catalyst (a metallocene olefin polymerization catalyst and / or a gas-phase biphenylphenol polymerization catalyst produced from a biphenylphenol polymerization precatalyst of Formula I) can be continuously fed to the reactor. A gas that is inert to the polymerization catalyst, such as nitrogen or argon, can be used to transport the polymerization catalyst to the reactor bed. Petition 870260054527, dated 05 / 06 / 2026, page 32 / 100 22 / 41

[0060] For the polymerization process, hydrogen can be used at a molar ratio between hydrogen gas and ethylene in the reactor that can be in a range of about 0.0 to 3.5, 0.0 to 1.0, in a range of 0.01 to 0.7, in a range of 0.03 to 0.5, in a range of 0.005 to 0.3 or in a range of 0.0017 to 0.0068. A number of embodiments utilize hydrogen gas.

[0061] Several aspects of the present revelation are provided as follows.

[0062] Aspect 1 provides an use of a supported gas-phase biphenylphenol polymerization catalyst to produce a polymer via a gas-phase polymerization process, wherein the supported gas-phase biphenylphenol polymerization catalyst is produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I: wherein each of R5, R7', R8 and R10 is independently a C1 to C20 alkyl, aryl, aralkyl, a halogen or a hydrogen; wherein each of R4 and R11 is independently a halogen or a hydrogen; wherein each of R2 and R13 is independently a C1 to C20 alkyl, aryl or aralkyl, or a hydrogen; wherein each of R15 and R16 is independently a 2,7-disubstituted carbazol-9-yl or a 3,6-disubstituted carbazol-9-yl; wherein L is a linear C3 or C4 alkylene that forms a 3-carbon bridge or a 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded; wherein each of R1, R3, R12 and R14 is independently a C1-C5 alkyl, a halogen or a hydrogen; wherein each of R6 and R9 is a hydrogen or a C1-C20 alkyl; wherein each X is independently a halogen, a hydrogen, a C1-C20 alkyl, an aralkyl Petition 870260054527, dated 05 / 06 / 2026, page 33 / 100 23 / 41 C7-C20, an aryl C6-C12 substituted by C1-C6 alkyl or a benzyl substituted by C1-C6 alkyl, -CH2Si(RC)3, where RC is a C1-C12 hydrocarbon; and where M is Zr or Hf.

[0063] Aspect 2 provides the use of Aspect 1, where each X is a methyl group.

[0064] Aspect 3 provides the use of Aspect 1 or 2, where each of R1, R3, R12 and R14 is a hydrogen.

[0065] Aspect 4 provides the use of Aspects 1, 2 or 3, wherein the gas-phase biphenylphenol polymerization precatalyst of Formula I is selected from a group consisting of the structures in (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix), as detailed in this document.

[0066] Aspect 5 provides the use of Aspects 1, 2 or 3, wherein the gas-phase biphenylphenol polymerization precatalyst is selected from a group consisting of structures in (iii) and (iv), as detailed in this document.

[0067] Aspect 6 provides the use of Aspect 1, wherein the polymer formed under conditions B (H2 / C2= 0.0017 and C6 / C2= 0.004 at 100 °C and 230 pounds per square inch (psi) of ethylene) has a molecular weight (Mw) in a range of about 150,000 daltons to about 1,200,000 daltons; or wherein the polymer formed under conditions K (H2 / C2= 0.0068 and C6 / C2= 0.004 at 100 °C and 230 psi) has a molecular weight (Mw) less than about 500,000 Daltons. That is, in one or more embodiments, the polymer has a molecular weight in the range of about 150,000 daltons to about 1,200,000 daltons under B conditions and a molecular weight less than about 500,000 under K conditions.

[0068] Aspect 7 provides a gas-phase polymerization catalyst system for producing a polymer via a gas-phase polymerization process, wherein the gas-phase polymerization catalyst comprises: a metallocene olefin polymerization catalyst; and the supported gas-phase biphenylphenol polymerization catalyst produced from the pre-catalyst of Petition 870260054527, dated 05 / 06 / 2026, page 34 / 100 24 / 41 gas-phase polymerization of biphenylphenol of Aspect 1. That is, in various embodiments, part or all of a polymerization catalyst system (e.g., the gas-phase metallocene and / or biphenylphenol polymerization precatalyst) is provided as a compensating solution. For example, a portion of the metallocene catalyst may be provided as a compensating solution. Alternatively, a portion of the gas-phase biphenylphenol polymerization precatalyst may be provided as a compensating solution.

[0069] Aspect 8 provides a gas-phase polymerization method for producing a polymer, wherein the method comprises: polymerizing an olefin monomer in a gas-phase polymerization reactor in the presence of the gas-phase polymerization catalyst system of Aspect 7 to produce the polymer.

[0070] Aspect 9 provides the gas-phase polymerization catalyst system of Aspect 7 or the gas-phase polymerization method of Aspect 8, wherein each R15 and R16 is a 3,6-di-t-butylcarbazol-9-yl.

[0071] Aspect 10 provides a polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, wherein the high and low molecular weight polyethylene components are produced together in a single gas phase reactor through a polymerization process employing the gas phase polymerization catalyst system of Aspect 7. Examples

[0072] Gas-phase biphenylphenol polymerization catalysts produced from the gas-phase biphenylphenol polymerization precatalyst of Formula (I), gas-phase polymerization catalyst systems including the gas-phase biphenylphenol polymerization catalysts, and comparative gas-phase polymerization catalysts (other than those produced from the gas-phase polymerization precatalyst of Formula (I)) were prepared as follows. Petition 870260054527, dated 05 / 06 / 2026, page 35 / 100 25 / 41

[0073] The gas-phase biphenylphenol polymerization precatalyst of structure (i) was prepared as follows. In a gloved chamber, a 16 oz oven-dried glass flask was loaded with hafnium chloride [HfCl4] (12.07 g, 37.7 mmol; available from Strem Chemical) and toluene (300 mL; available from Fisher Scientific) and a magnetic stir bar. The contents of the flask were cooled to approximately -30 degrees Celsius (°C). Methylmagnesium bromide (56.6 mL of 2.6 M solution in diethyl ether, 147 mmol; available from Millipore Sigma) was added and the solution was stirred for 15 minutes at -30 °C. The flask was loaded with a ligand of structure A (56.00 g, 35.9 mmol). The binder for structure A was prepared as described in document WO 2017 / 058.981, and the complete content of document WO 2017 / 058.981 is incorporated herein by reference.The contents of the flask were left under agitation for 3 hours as the solution gradually warmed to room temperature. The mixture was filtered and the solvent was removed in vacuo from the filtrate to obtain a gray powder (45 g, 71.0% yield). The presence of the gas-phase biphenylphenol polymerization precatalyst of structure (i) was confirmed by 1H NMR analysis. 1H NMR (400 MHz, Benzene-d6) δ 8.19 (d, 2H), 8.01 (s, 2H), 7.99 (d, 2H), 7.89 (d, 2H), 7.74 (s, 2H), 7.64 (d, 2H), 7.55 (s, 2H), 7.51 (dd, 2H), 7.31 (dd, 2H), 7.06 (m, 2H), 3.68 (m, 2H), 3.42 (m, 2H), 1.79 (d, 2H), 1.67 (d, 2H), 1.60 (s, 18H), 1.47 (s, 6H), 1.42 (s, 6H), 1.35 (s, 6H), 1.33 - 1.25 (m, 26H), 1.25 (s, 18H), 0.93 (t, 6H), 0.92 (s, 18H), 0.59 (m, 4H), 0.10 (s, 6H), 0.07 (s, 6H), -0.82 (s, 6H). —Si Si— —Si Si— n-Ocf / n-Oct n-Ocf n-Oct (Structure A) (Structure i) Petition 870260054527, dated 05 / 06 / 2026, p. 36 / 100 26 / 41

[0074] As used in this document, Me refers to methyl, n-Oct refers to n-C8H17 and n-Pr refers to n-C3H7.

[0075] The gas-phase biphenylphenol polymerization precatalyst of Formula (ii) was prepared using the same components and methodology as the gas-phase biphenylphenol polymerization precatalyst of structure (i), but using zirconium chloride [ZrCl4] (15.0 g, 64.1 mmol) instead of hafnium chloride (99.9 g; 92.9% yield). The presence of the gas-phase biphenylphenol polymerization precatalyst of structure (ii) was confirmed by 1H NMR analysis. 1H NMR (400 MHz, Benzene-d6) δ 8.19 (d, 2H), 8.01 (s, 2H), 7.99 (d, 2H), 7.87 (d, 2H), 7.79 (d, 2H), 7.65 (d, 2H), 7.57 (d, 2H), 7.51 (dd, 2H), 7.30 (dd, 2H), 7.04 (m, 2H), 3.57 (m, 2H), 3.43 (m, 2H), 1.79 (d, 2H), 1.67 (d, 2H), 1.60 (s, 18H), 1.46 (s, 6H), 1.42 (s, 6H), 1.35 (s, 6H), 1.34 - 1.25 (m, 26H), 1.25 (s, 18H), 0.94 (t, 6H), 0.93 (s, 18H), 0.60 (m, 4H), 0.11 (s, 6H), 0.08 (s, 6H), -0.63 (s, 6H). (Structure A) (Structure ii)

[0076] The gas-phase biphenylphenol polymerization precatalyst of structure (iii) was prepared as follows. In a gloved chamber, a 4 oz oven-dried glass flask was loaded with zirconium chloride [ZrCl4] (0.186 g, 0.80 mmol; available from Strem Chemical) and toluene (30 mL; available from Fisher Scientific) and a magnetic stir bar. The contents of the flask were cooled to approximately -30 degrees Celsius (°C). Methylmagnesium bromide (1.12 mL of 3.0 M solution in diethyl ether, 3.34 mmol; available from Millipore Sigma) was added and the solution was stirred for 2 minutes at -30 °C. The flask was loaded Petition 870260054527, dated 05 / 06 / 2026, p. 37 / 100 27 / 41 with a structure B ligand (1.00 g, 0.80 mmol). The structure B ligand was prepared as described in WO 2014 / 105411, and the full contents of WO 2014 / 105411 are incorporated herein by reference. The contents of the vial were stirred for 2 hours as the solution gradually warmed to room temperature. The mixture was filtered and the solvent was removed under vacuum from the filtrate to obtain a grey powder, which was washed with 20 mL of hexane and isolated by filtration (0.954 g, 87.1% yield). The presence of the gas-phase biphenylphenol polymerization precatalyst of structure (iii) was confirmed by 1H NMR analysis.RMN1H (400 MHz, Benzeno-d6) δ 8.20 (d, 2H), 8.09 (d, 2H), 7.90 (d, 2H), 7.82 (d, 2H), 7.80 (d, 2H), 7.50 (dd, 2H), 7.37 (dd, 2H), 7.33 (d, 2H), 6.89 (dd, 2H), 6.12 (dd, 2H), 3.35 (m, 2H), 3.20 (m, 2H), 1.72 (d, 2H), 1.58 (s, 18H), 1.57 (d, 2H), 1.28 (s, 18H), 1.27 (s, 6H), 1.23 (s, 6H), 1.14 (s, 6H), 0.88 (s, 18H), -0.58 (s, 6H). (Estrutura B) (Estrutura iii)

[0077] The gas-phase biphenylphenol polymerization precatalyst of structure (i) was prepared as follows. A 3.22 M methylmagnesium bromide solution (0.57 mL, 1.83 mmol) was added to a suspension of ZrCl4 (102 mg, 0.44 mmol) in toluene (20 mL) at -28 °C. The solution was stirred for 2 min, during which time a dark red color was formed. The ligand of structure C (550 mg, 0.44 mmol) was then added in a portion as a solution in toluene (10 mL). The ligand of structure C was prepared as described in document 20160108156A1, and the complete contents of document 20160108156A1 are incorporated herein by way of reference. Petition 870260054527, dated 05 / 06 / 2026, page 38 / 100 28 / 41 reference. The solution was allowed to warm to room temperature and stirred for a total of 4 hours. Hexane (30 mL) was added and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure. The crude solid was then reheated in hot toluene (20 mL) and filtered. The filtrate was evaporated under reduced pressure to provide 562 mg (93%) of a pale yellow solid. The presence of the gas-phase biphenylphenol polymerization precatalyst of structure (iv) was confirmed by 1H NMR analysis.RMN 1H (400 MHz, C6D6, 298 K) δ 8,19 (d, J = 8,0 Hz, 1H), 8,15 (d, J = 8,0 Hz, 2H), 7,73 (s, 1H), 7,66 (s, 1H), 7,60 (d, J = 8,0 Hz, 2H), 7,49-7,39 (m, 4H), 7,30 (d, J = 8,0 Hz, 1H), 7,20 (s, 1H), d (J = 8,0 Hz, 1H), 7,06-7,00 (m, 3H), 6,63 (d, J = 8,0 Hz, 1H), 6,22 (dd, J = 8,0 Hz e 4,0 Hz, 1H), 5,75 (td, J = 8,0 Hz e 4,0 Hz, 1H), 3,62 (t, J = 8,0 Hz, 1H), 3,30 (m, 2H), 3,16 (m, 1H), 1,61 (s, 12H), 1,47 (s, 12H), 1,26 (s, 18H), 1,25 (s, 18H), 0,93 (s, 12H), 0,84 (s, 12H), 0,52 (d, 12,0 Hz, 3H), -0,56 (s, 3H), -0,98 (s, 3H). (Estrutura C) (Estrutura iv)

[0078] A gas-phase biphenylphenol polymerization precatalyst of structure (v) was prepared as follows. To a suspension of ZrCl4 (104 mg, 0.45 mmol) in toluene (20 mL) at -28 °C, a 3.22 M solution of methylmagnesium bromide in diethyl ether (0.61 mL, 1.97 mmol) was added. The solution was stirred for 2 min, during which a dark red color was formed. The ligand of structure D (550 mg, 0.45 mmol) was then added in a portion as a solution in toluene (10 mL). The ligand of Formula B was prepared as described in document US20160108156(A1), and the full contents of document US20160108156(A1) are Petition 870260054527, dated 05 / 06 / 2026, page 39 / 100 29 / 41 incorporated herein for reference.

[0079] The solution was allowed to warm to room temperature and stirred for a total of 4 hours. Hexanes (30 mL) were added and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure, yielding 600 mg (99%) of a pale yellow solid. The presence of the gas-phase biphenylphenol polymerization precatalyst of structure (v) was confirmed by 1H NMR analysis. 1H NMR (400 MHz, C6D6, 298 K) δ 8.15 (d, J = 8.0 Hz, 2H), 8.07 (dd, J = 8.0 and 4.0 Hz, 2H), 7.71 (d, J = 4.0 Hz, 2H), 7.68 (d, J = 4.0 Hz, 2H), 7.67 (d, J = 4.0 Hz, 2H), 7.36 (t, J = 4.0 Hz, 2H), 7.33 (t, J = 4.0 Hz, 2H), 7.29 (d, J = 4.0 Hz, 2H), 7.03-7.01 (m, 3H), 6.99 (d, J = 4.0 Hz, 1H), 6.63 (m, 2H) (Structure D) (Structure V)

[0080] The gas-phase biphenylphenol polymerization precatalyst of structure (i) was prepared as follows. A 3.22 M methylmagnesium bromide solution (0.40 mL, 1.30 mmol) was added to a suspension of ZrCl4 (69 mg, 0.30 mmol) in toluene (20 mL) at -28 °C. The solution was stirred for 2 min, during which time a dark red color was formed. The ligand of structure E (513 mg, 0.30 mmol) was then added in a portion as a solution in toluene (10 mL). The ligand of structure E was prepared as described in document WO2017058981A1, and the complete contents of document WO2017058981A1 are incorporated herein by reference. The solution was allowed to warm to room temperature and stirred for Petition 870260054527, dated 05 / 06 / 2026, page 40 / 100 30 / 41 a total of 3 hours. Hexanes (30 mL) were added and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure yielding 495 mg (90%) of a pale yellow solid. The presence of the gas-phase biphenylphenol polymerization precatalyst of structure (vi) was confirmed by 1H NMR analysis. 1H NMR (400 MHz, C6D6, 298 K) δ 8.27 (d, J = 8.0 Hz, 2H), 8.16 (d, J = 8.0 Hz, 2H), 8.05 (s, 2H), 7.96 (s, 2H), 7.63 (d, J = 8.0 Hz, 2H), 7.56 (d, J = 8.0 Hz, 2H), 6.92 (d, J = 4.0 Hz, 2H), 6.79 (d, J = 4.0 Hz, 2H), 6.77 (d, J = 4.0 Hz, 2H), 6.13 (d, J = 4.0 Hz, 1H), 6.11 (d, J = 4.0 Hz, 1H), 3.54 (q, J = 4.0 Hz, 2H), 3.30 (q, J = 4.0 Hz, 2H), 2.13 (s, 6H), 1.66-0.89 (m, 130H), -0.42 (s, 6H). (Structure E) (Structure vi)

[0081] The gas-phase biphenylphenol polymerization precatalyst of structure (vii) was prepared as follows. Petition 870260054527, dated 05 / 06 / 2026, p. 41 / 100 31 / 41

[0082] Synthesis of l-(4-bromobutoxy)-4-fluoro-2-iodobenzene: A three-necked round-bottom flask fitted with a stirring rod, septa, a condenser, and a nitrogen gas inlet was charged with 4-fluoro-2-iodophenol (3.20 g, 13.45 mmol, preparation published in US document 2015 / 0291713A1), anhydrous potassium carbonate (3.79 g, 27.45 mmol), 1,4-dibromobutane (28 mL, 234.47 mmol), and acetone (92 mL). The mixture was stirred under reflux for 3 hours and then allowed to cool naturally to room temperature. The mixture was filtered, the solids were washed with acetone, and the filtrate was concentrated by rotary evaporation to remove acetone. To remove excess 1,4-dibromobutane, the remaining yellow solution was heated to 60 °C and distilled under high vacuum using a short path distillation head while slowly increasing the temperature to yield 4.45 g (88.8%) of the product as a light brown oil.

[0083] NMR Ή (400 MHz, CDC13) δ 7.48 (dd, J = 7.6, 3.0 Hz, 1H), 7.00 (ddd, J = 9.0, 7.8, 3.0 Hz, 1H), 6.71 (dd, J = 9.0, 4.6 Hz, 1H), 3.99 (t, J = 5.9 Hz, 2H), 3.53 (t, J = 6.6 Hz, 2H), 2.18 - 2.09 (m, 3H), 2.02 - 1.94 (m, 2H). RMN13C (101 MHz, CDC13) δ 156.64 (d, J = 244.0 Hz), 153.93 (d, J = 2.2 Hz), 125.94 (d, J = 25.0 Hz), 115.48 (d, J = 22.7 Hz), 112.05 (d, J = 8.2 Hz), 85.94 (d, J = 8.3 Hz), 68.74, 33.54, 29.42, 27.63. RMN19F (376 MHz, CDCI3) δ -122.33 (td, J = 7.9, 4.8 Hz).

[0084] Synthesis of 5-fluoro-2-(2-(4-fluoro-2-iodophenoxy)ethoxy)-1-iodo-3-methylbenzene: A three-necked round-bottom flask equipped with a stirring rod, septa, a condenser, and a nitrogen gas inlet was charged with 1-(4-bromobutoxy)-4-fluoro-2-iodobenzene (3.66 g, 9.81 mmol), 4-fluoro-2-iodo-6 Petition 870260054527, dated 05 / 06 / 2026, p. 42 / 100 32 / 41 methylphenol (2.47 g, 9.82 mmol, preparation published in US 2015 / 0291713A1), anhydrous potassium carbonate (2.87 g, 20.76 mmol), and acetone (66 mL). The mixture was stirred under reflux for 5.5 hours and then allowed to cool naturally to room temperature. The mixture was filtered, the solids were washed with acetone, and the filtrate was concentrated by rotary evaporation to yield a dark red crude oil (5.30 g). The oil was dissolved in a minimal amount of hexanes and purified by flash column chromatography (ISCO, 330 g silica gel, 0 to 5% ethyl acetate in hexanes). The fractions containing the product were combined and concentrated by rotary evaporation to yield a yellow oil. To remove traces of ethyl acetate, the oil was dissolved in dichloromethane and concentrated by rotary evaporation to produce a yellow oil (repeated twice).The oil was dried under high vacuum to yield 4.33 g (81.2%) of the product as a yellow oil.

[0085] 1H NMR (400 MHz, CDCb) δ 7.50 (dd, J = 7.6, 3.0 Hz, 1H), 7.31 (ddd, J = 7.5, 3.0, 0.7 Hz, 1H), 7.01 (ddd, J = 9.0, 7.8, 3.0 Hz, 1H), 6.91 - 6.85 (m, 1H), 6.76 (dd, J = 9.0, 4.6 Hz, 1H), 4.12 - 4.05 (m, 2H), 3.95 - 3.88 (m, 2H), 2.32 (s, 2H), 2.14 - 2.09 (m, 4H). NMR13C (101 MHz, CDCb) δ 158.71 (d, J = 168.7 Hz), 156.27 (d, J = 165.2 Hz), 154.13 (d, J = 1.9 Hz), 153.41 (d, J = 1.5 Hz), 133.04 (d, J = 8.3 Hz), 125.95 (d, J = 24.9 Hz), 123.28 (d, J = 24.8 Hz), 117.84 (d, J = 22.2 Hz), 115.51 (d, J = 22.6 Hz), J = 8.1 Hz), 91.35 (d, J = 9.5 Hz), 86.07 (d, J = 8.7 Hz), 72.45 (d, J = 1.4 Hz), 69.61, 26.91, 26.00, 17.30 (d, J = 19.5 Hz NMR (39.6 Hz). CDCb) δ −118.22 (t, J = 8.1 Hz), -122.40 (td, J = 7.6, 4.5 Hz). 1. Pd(PPh3)4NaOH, H20 THF, DME 2. PTSA, MeOH (F-structure) Petition 870260054527, dated 05 / 06 / 2026, page 43 / 100 33 / 41

[0086] The reaction was set up in a gloved chamber under a nitrogen atmosphere. A flask was loaded with zirconium tetrachloride (0.037 g, 0.16 mmol) and toluene (10 mL). The fluid paste mixture was cooled to -25 °C in the freezer of the gloved chamber. To the cooled fluid paste mixture, 3.0 M methylmagnesium bromide in diethyl ether (0.25 mL, 0.75 mmol) was added. The mixture was stirred for about 4 minutes. The solid went into solution and turned brown. The F-structure ligand (0.20 g, 0.16 mmol) was added to the mixture as a solid. The resulting mixture was stirred at room temperature for 5 h. Hexane (10 mL) was then added to the mixture and filtered. The solution was concentrated under vacuum to yield 0.25 g (total conversion) of the product as a light yellow solid. The excess mass was attributed to the presence of residual toluene, as observed by proton NMR in combination with the total conversion.The presence of the gas-phase biphenylphenol polymerization precatalyst of structure (vii) was confirmed by 1H NMR analysis. 1H NMR (400 MHz, Benzene-d6) δ 8.18 (d, J = 8.2 Hz, 1H), 8.15 (d, J = 8.2 Hz, 1H), 8.08 (d, J = 8.3 Hz, 1H), 7.88 (d, J = 1.7 Hz, 1H), 7.80 (d, J = - 6.90 (m, 2H), 6.55 (ddd, J = 9.0, 7.1, 3.2 Hz, 1H), 6.14 (dd, J = 8.5, 3.2 Hz, 1H), 5.15 (dd, J = 9.1, 4.9 Hz, 1H), 4.44 (t, J = 11.7 Hz, 1H), 3.91 - 3.70 (m, 2H), 3.37 (dd, J = 11.0, 7.6 Hz, 1H), 1.78 (d, J = 14.5 Hz, 1H), 1.68 - 1.52 (m, 2H), 1.47 (s, 9H), 1.37 (s, 9H), 1.25 (s, 10H), 1.24 (s, 9H), 1.21 (s, 4H), 1.14 (s, 3H), 1.13 (s, 3H), 0.89 (s, 9H), 0.83 (s, 3H), 0.81 (s, 10H), -0.70 (s, 3H), -1.03 (s, 3H). Me. ,Me(Structure vii) Petition 870260054527, dated 05 / 06 / 2026, p. 44 / 100 34 / 41

[0087] The gas-phase biphenylphenol polymerization precatalyst of structure (viii) was prepared as described in US document 9000108B2, and the complete contents of US document 9000108B2 are incorporated herein by reference.

[0088] The gas-phase biphenylphenol polymerization precatalyst of structure (ix) was prepared as described in US document 9029487B2, and the complete contents of US document 9029487B2 are incorporated herein by reference. (Structure ix)

[0089] Comparative gas-phase polymerization catalysts (other than those produced from gas-phase polymerization precatalyst of Formula (I)) were prepared as follows. The comparative catalysts may include a branched or substituted bridge. For example, as illustrated in structures (x) and (xi), the comparative catalyst may include a branched or substituted bridge formed between two oxygen atoms.

[0090] The gas-phase biphenylphenol polymerization precatalyst of structure (x) was prepared as described in document US20170137550A1, and the complete contents of document US20170137550A1 are incorporated herein by way of Petition 870260054527, dated 05 / 06 / 2026, page 45 / 100 Reference 35 / 41.

[0091] The comparative polymerization precatalyst of structure (xi) was prepared according to the procedure described in document US20170137550A1, and the complete content of document US20170137550A1 is incorporated herein by reference.

[0092] In several embodiments, gas-phase biphenylphenol polymerization catalysts produced from the precatalysts of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix) can be employed to produce a polymer.

[0093] Example 1 (EX1), an activated and supported gas-phase biphenylphenol polymerization catalyst of Formula I was prepared as follows. In a nitrogen-purged glove chamber, an oven-dried glass bottle was loaded with 2.65 grams (g) of treated pyrolyzed silica (CABOSIL TS-610; available from WR Grace) in a flowable paste in 75 g of toluene (available from Aldrich), and a stirring rod was used and stirred until well dispersed. 22 g of a 10% by weight methylaluminoxane (MAO) solution (available from WR Grace as 10% by weight in toluene) were added to the bottle to make a mixture. A Petition 870260054527, dated 05 / 06 / 2026, p. 46 / 100 The 36 / 41 mixture was magnetically stirred for 15 minutes, then the gas-phase biphenylphenol polymerization precatalyst of structure i (0.303 g) was added and the mixture was stirred for 30 to 60 minutes. The mixture was spray-dried using a Buchi Mini Spray B-290 dryer with the following parameters to produce the dry, supported, and activated gas-phase biphenylphenol polymerization catalyst of Example 1: Set temperature - 185 °C, outlet temperature - 100 °C (min.), vacuum - 95 and pump speed - 150 rpm.

[0094] Example 2 (EX2) was prepared in the same manner as Example 1 with the change that the activated and supported gas-phase biphenylphenol polymerization catalyst of Example 2 was used, as indicated in Table 1.

[0095] Example 3 (EX3) was prepared in the same manner as Example 1 with the change that the activated and supported gas-phase biphenylphenol polymerization catalyst of Example 3 was used, as indicated in Table 1.

[0096] Example 4 (EX4) was prepared in the same manner as Example 1 with the change that the activated and supported gas-phase biphenylphenol polymerization catalyst of Example 4 was used, as indicated in Table 1.

[0097] Example 5 (EX5) was prepared in the same manner as Example 1 with the change that the activated and supported gas-phase biphenylphenol polymerization catalyst of Example 5 was used, as indicated in Table 1.

[0098] Example 6 (EX6) was prepared in the same manner as Example 1 with the change that the activated and supported gas-phase biphenylphenol polymerization catalyst of Example 6 was used, as indicated in Table 1.

[0099] Example 7 (EX7) was prepared in the same manner as Example 1 with the change that the activated and supported gas-phase biphenylphenol polymerization catalyst of Example 7 was used under the conditions as indicated in Table 1.

[00100] Example 8 (EX8) was prepared in the same way as Example 1 with the change that the activated gas-phase biphenylphenol polymerization catalyst and Petition 870260054527, dated 05 / 06 / 2026, page 47 / 100 37 / 41 of the supported data from Example 8 was used, as indicated in Table 1.

[00101] Example 9 (EX9) was prepared in the same manner as Example 1 with the change that the activated and supported gas-phase biphenylphenol polymerization catalyst of Example 9 was used, as indicated in Table 1.

[00102] Comparative Example 1 (EC1) was prepared in the same way as Example 1 with the change that the catalyst from Comparative Example 1 was used, as indicated in Table 1.

[00103] Comparative Example 2 (CE2) was prepared in the same way as CE1 with the change that the catalyst for Comparative Example 2 was prepared under the conditions as indicated in Table 1.

[00104] Comparative Example 3 (EC3) was prepared in the same way as Example 1 with the change that the catalyst from Comparative Example 1 was used, as indicated in Table 1.

[00105] Comparative Example 4 (EC4) was prepared in the same way as EC3 with the change that the catalyst of Comparative Example 4 was prepared under the conditions as indicated in Table 1.

[00106] The ethylene / 1-hexene copolymerizations of each of the individual catalysts from EX1 to 9 and EC1 were carried out in the gas phase in a 2 L semi-batch autoclave polymerization reactor equipped with a mechanical stirrer as follows. The reactor was first dried for 1 hour, charged with 200 g of sodium chloride (NaCl) and dried by heating at 100 °C under nitrogen for 30 minutes. After drying, 5 grams of silica-supported methylaluminoxane (SMAO) were introduced as a nitrogen-pressurized stripper. After adding the SMAO, the reactor was sealed and the components were stirred. The reactor was then charged with hydrogen (H2 pre-charge, as indicated below for each condition) and hexene (C6 / C2 ratio, as indicated below for each condition), then pressurized with ethylene (230 psi). Once the system has reached a steady state, the type and quantity of Petition 870260054527, dated 05 / 06 / 2026, page 48 / 100 38 / 41 of the respective activated catalyst, as identified in Tables 1 and 2 for each EX1 to 9 and EC1, was loaded into the reactor at 80 °C to initiate polymerization. The reactor temperature was brought up to 90 or 100 °C and maintained at this temperature throughout the 1-hour pass. The passes were conducted under Condition B or K as detailed below in Table 1. At the end of the pass, the reactor was cooled, vented, and opened. The resulting product mixture was washed with water and methanol, then dried. The results for EX1 to 9 and for EC1 are shown in Tables 1 and 2.

[00107] In several embodiments, the gas-phase biphenylphenol polymerization catalysts produced from the pre-catalyst of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix) can be employed in the gas-phase polymerization catalyst systems in the present invention to produce a high molecular weight polyethylene component in a multimodal (e.g., bimodal) polyethylene composition.

[00108] The Mn (number average molecular weight) and Mw (weight average molecular weight), the average molecular weight z (Mz) were determined by gel permeation chromatography (GPC), as is known in the art.

[00109] Productivity (kilograms of polymer / kilograms of catalyst) was determined as the ratio between the polymer produced and the amount of catalyst and activator added to the reactor.

[00110] The melting temperature (i.e., Tm) can be determined by differential scanning calorimetry according to ASTM D 3418-08. For example, using a scan rate of 10 °C / min on a 10 mg sample and using the second heating cycle.

[00111] The comonomer content (i.e., 1-hexene) incorporated into the polymers (% by weight) can be determined by fast FT-IR spectroscopy on the polymer dissolved in a GPC measurement.

[00112] Conditions B are as follows: Temperature = 100 °C; Ethylene = 230 Petition 870260054527, dated 05 / 06 / 2026, page 49 / 100 39 / 41 pounds per square inch (psi); H2 / C2 = 0.0017; C6 / C2 = 0.004.

[00113] The conditions for K are as follows: Temperature = 100 °C; Ethylene = 230 psi; H2 / C2 = 0.0068; C6 / C2 = 0.004. Table 1 Pre-catalyst structure Conditions Cat. Load (mg) Cat. Prod. (gPE / gcat / h) EX1 i B 1.6 28248 EX2 ii B 1.2 39081 EX3 iii B 0.7 183.282 EX4 iv B 15.4 26.532 EX5 v B 1.2 3500 vii EX5.6 vi 2967 EX8 viii B 5.2 15846 EX9 ix B 12 1754 EC1 x B 15.1 11053 EC2 x K 14.3 4112 EC3 xi B 15.3 2379 EC4 xi K 15.5 3226 Table 2 Structure of pre-catalyst Mn (Da) Mw (Da) Mw / Mn Tm (°C) EX1 i 149.849 523.102 da 3.49 127.1 EX2 ii 54.478 251.152 da 4.61 89.61 ii from 2.86 122.7 EX4 iv 32.365 205.275 6.34 124.3 EX5 v 139.957 515.608 3.68 N / A EX6 vi 64.498 950.294 EX6 1 28.365 vi 619.530 by 2.53 125.8 EX8 viii 12.702 145.159 by 11.43 120.2 EX9 ix 187.700 678.100 by 3.6 117.8 EC1 x N / 0.A0+UHM0 123.95 EC2 x N / A UHMW (2,000,000+) N / A 128.56 EC3 xi N / A UHMW (2,000,000+) N / A 122.63 EC4 xi N / A UHMW (2,000,0001+) N / A

[00114] Ultra-high molecular weight (UHMW) refers to a single-chain polyethylene polymer with a polyethylene equivalent molecular weight of 2,000,000 daltons or greater, as measured by conventional GPC. That is, in Table 2, UHMW is shown for those polymers with ultra-high molecular weights that could not be Petition 870260054527, dated 05 / 06 / 2026, page 50 / 100 40 / 41 measured accurately by the GPC test method (e.g., due to low polymer solubility, line clogging, unsatisfactory mass recoveries, or other analytical problems typically found in polyethylene polymers with molecular weights of more than two million daltons).

[00115] As detailed in Tables 1 and 2, EX 1 to 9 provide the use of a supported gas-phase biphenylphenol polymerization catalyst to produce a polymer via a gas-phase polymerization process, wherein the supported gas-phase biphenylphenol polymerization catalyst is produced from a gas-phase biphenylphenol polymerization precatalyst of Formula I.

[00116] The polymers resulting from EX 1 to 9 have an improved (i.e., lower) molecular weight than polymers produced from comparative catalysts under similar conditions. For example, each of EX 1 to 9 provides a polymer having a molecular weight in the range of 150,000 daltons to 1,200,000 daltons under B conditions and / or having a value less than 500,000 daltons under K conditions, which may be desirable for certain applications. For example, each of the supported gas-phase biphenylphenol polymerization catalysts from EX 1 to 9 can be employed with a metallocene olefin polymerization catalyst to produce a gas-phase polymerization catalyst system that can be used in a single gas-phase polymerization reactor to produce a multimodal (e.g., bimodal) polymer.

[00117] The gas-supported biphenylphenol polymerization catalyst of Formula I can be used to produce a polymer via a gas-phase polymerization process that has improved comonomer incorporation compared to the amount of comonomer incorporation in a polymer produced via a solution-phase polymerization process using a biphenylphenol polymerization catalyst of Formula I (e.g., the same supported gas-phase biphenylphenol polymerization catalyst of Formula I). ​​The supported gas-phase biphenylphenol polymerization catalyst of Formula I Petition 870260054527, dated 05 / 06 / 2026, page 51 / 100 41 / 41 can be used to produce a polymer via a gas-phase polymerization process that has improved comonomer incorporation compared to the amount of comonomer incorporation in a polymer produced from a comparative gas-phase catalyst under similar gas-phase conditions.

Claims

1. Use of a supported gas-phase biphenylphenol polymerization catalyst to produce both (i) a polymer via a gas-phase polymerization process, formed under B conditions of H2 / C2 = 0.0017 and C6 / C2 = 0.004 at 100°C and 230 psi of ethylene, having a molecular weight (Mw) in the range of 150,000 Daltons to 1,200,000 Daltons, and (ii) a polymer via a gas-phase polymerization process, formed under K conditions of H2 / C2 = 0.0068 and C6 / C2 = 0.004 at 100°C and 230 psi of ethylene, having an Mw less than 500,000 Daltons, characterized in that the supported gas-phase biphenylphenol polymerization catalyst is produced from a precatalyst for gas-phase polymerization of biphenylphenol selected from a group consisting of the structures in (ii), (vi), and (vii): Petition 870260054527, dated 05 / 06 / 2026, page 53 / 100 2 / 2 (vii) 2. Gas-phase polymerization method for producing both a polymer (a) having a molecular weight (Mw) in the range of 150,000 Daltons to 1,200,000 Daltons, and a polymer (b) having an Mw less than 500.000 Daltons, the method being characterized by comprising: - polymerizing an olefin monomer in a gas-phase polymerization reactor in the presence of a gas-phase polymerization catalyst system comprising a metallocene olefin polymerization catalyst; and - the supported gas-phase biphenylphenol polymerization catalyst produced from the gas-phase biphenylphenol polymerization precatalyst as defined in claim 1, wherein to prepare polymer (a) the gas-phase polymerization is carried out under B conditions of H2 / C2 = 0.0017 and C6 / C2 = 0.004 at 100°C and 230 psi of ethylene, and to prepare polymer (b) the gas-phase polymerization is carried out under K conditions of H2 / C2 = 0.0068 and C6 / C2 = 0.004 at 100°C and 230 psi.