Gas-phase diphenol polymerization catalyst

Abstract

An embodiment relates to the use of a supported gas-phase diphenol polymerization catalyst for preparing a polymer via a gas-phase polymerization process, wherein the supported gas-phase diphenol polymerization catalyst is made of a gas-phase diphenol polymerization precatalyst of Formula I.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to gas phase biphenol polymerization catalysts, and more particularly, gas phase biphenol polymerization catalysts useful for preparing polymers via a gas phase polymerization process. Background Art

[0002] The polymers are useful in a variety of products including, for example, films, fibers, nonwoven and / or woven fabrics, extruded and / or molded articles, etc. The polymers may 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] The present disclosure provides various embodiments, including:

[0004] A use of a supported gas-phase diphenol polymerization catalyst for preparing a polymer via a gas-phase polymerization process, wherein the supported gas-phase diphenol polymerization catalyst is prepared from a gas-phase diphenol polymerization precatalyst of formula I:

[0005]

[0006] Where R 5 , R 7- , R 8 and R 10 Each of which is independently (C1 to C 20 ) alkyl, aryl, aralkyl, halogen or hydrogen; wherein R 4 and R 11 Each of is independently halogen or hydrogen; wherein R 2 and R 13 Each of C1 to C 20 alkyl, aryl or aralkyl or hydrogen; wherein R 15 and R 16 Each of the following is independently a 2,7-disubstituted carbazole-9-yl group or a 3,6-disubstituted carbazole-9-yl group; wherein L is a straight-chain C3 or C4 alkylene group, which forms a 3-carbon bridge or a 4-carbon bridge between the two oxygen atoms covalently bonded to L, respectively; wherein R 1 , R 3 , R 12 and R 14 Each of the following is independently (C1-C8)alkyl, halogen or hydrogen; wherein R 6 and R 9 Each of which is hydrogen or (C1-C8) alkyl; wherein each X is independently halogen, hydrogen, (C1-C 20 ) alkyl, (C7-C 20 )aralkyl, (C1-C6)alkyl-substituted (C6-C 12)aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R C )3, where R C It is C1-C 12 hydrocarbon; and wherein M is zirconium (Zr) or hafnium (Hf). DETAILED DESCRIPTION

[0007] A supported gas phase diphenol polymerization catalyst that can be used to prepare a polymer via a gas phase polymerization process is made from a gas phase diphenol polymerization precatalyst of formula I:

[0008]

[0009] Where R 5 , R 7- , R 8 and R 10 Each of which is independently (C1 to C 20 ) alkyl, aryl, aralkyl, halogen or hydrogen; wherein R 4 and R 11 Each of is independently halogen or hydrogen; wherein R 2 and R 13 Each of C1 to C 20 alkyl, aryl or aralkyl or hydrogen; wherein R 15 and R 16 Each of the following is independently a 2,7-disubstituted carbazole-9-yl group or a 3,6-disubstituted carbazole-9-yl group; wherein L is a straight-chain C3 or C4 alkylene group, which forms a 3-carbon bridge or a 4-carbon bridge between the two oxygen atoms covalently bonded to L, respectively; wherein R 1 , R 3 , R 12 and R 14 Each of the following is independently (C1-C8)alkyl, halogen or hydrogen; wherein R 6 and R 9 Each of which is hydrogen or (C1-C8) alkyl; wherein each X is independently halogen, hydrogen, (C1-C 20 ) alkyl, (C7-C 20 )aralkyl, (C1-C6)alkyl-substituted (C6-C 12 )aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R C )3, where R C It is C1-C 12 A hydrocarbon; and wherein M is Zr or Hf.

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

[0011] As mentioned, R as shown in Formula I 5 , R 7- , R 8 and R 10 Each of the above may be independently (C1 to C 20 ) alkyl, aryl, aralkyl, halogen or hydrogen. One or more embodiments provide that: R 5 , R 7- , R 8 and R 10 At least one of is a halogen, such as fluorine. One or more embodiments provide that: R 5 , R 7- , R 8 and R 10 Each of is a halogen, such as fluorine. One or more embodiments provide that: R 5 and R 10 Each of is a halogen, such as fluorine. One or more embodiments provide that: R 5 and R 10 At least one of is an alkyl- or aryl-substituted silyl group. One or more embodiments provide that: R 5 and R 10 Each of is a dialkyl or trialkyl substituted silyl group. One or more embodiments provide that: R 5 and R 10 Each of is octyldimethylsilyl.

[0012] One or more embodiments provide that: wherein R 1 , R 3 , R 12 and R 14 Each of is independently (C1-C8) alkyl, halogen or hydrogen. One or more embodiments provide that: R 1 , R 3 , R 12 and R 14 At least one of is hydrogen. One or more embodiments provide that: R 1 , R 3 , R 12 and R 14 Each of is hydrogen.

[0013] One or more embodiments provide that: R7 and R 8 At least one of is hydrogen. One or more embodiments provide that: R 7 and R 8 Each of is hydrogen. One or more embodiments provide that: R 7 and R 8 At least one of is C1 alkyl, such as methyl. One or more embodiments provide that: R 7 and R 8 Each of is methyl.

[0014] One or more embodiments provide that: R 6 and R 9 Each of is hydrogen or (C1-C8) alkyl. One or more embodiments provide that: R 6 and R 9 Each of is hydrogen.

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

[0016] As used herein, "aryl" includes phenyl, naphthyl, pyridyl and other groups, whose molecules have a ring structure unique to benzene, naphthalene, phenanthrene, anthracene, etc. It should be understood that "aryl" can be C6 to C 20 Aryl. For example, a C6H5-aromatic structure is a "phenyl" and a -C6H4-aromatic structure is a "phenylene". As used herein, an "aralkyl" is an alkyl group with a pendant aromatic group, and may also be referred to as an "arylalkyl". It should be understood that an "aralkyl" can be C7 to C 20 Aralkyl. "Alkaryl" is an aryl group having one or more pendant alkyl groups. As used herein, "hydrocarbyl" includes aliphatic, cyclic, olefinic, acetylenic, and aromatic groups (ie, hydrocarbyl groups) that include hydrogen and carbon lacking one hydrogen.

[0017] As described above, R as shown in Formula I 4 and R 11 Each of may independently be hydrogen or a halogen, such as fluorine. For example, one or more embodiments provide that: R 4 and R 11 Each of is hydrogen.

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

[0019] As described above, R as shown in Formula I 15 and R 16 Each of may be a 2,7-disubstituted carbazole-9-yl group or a 3,6-disubstituted carbazole-9-yl group. For example, one or more embodiments provide that: R 15 and R 16 Each of is a 2,7-disubstituted carbazole-9-yl selected from 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 provide that: R 15 and R 16 Each of the above is a 3,6-disubstituted carbazole-9-yl group selected from 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 described above, as shown in Formula I, L can be a straight chain C3 or C4 alkylene group, which forms a 3-carbon bridge or a 4-carbon bridge, respectively, between two oxygen atoms covalently bonded to L. For example, in one or more embodiments, L can be a saturated (C3-C4) alkyl group, which forms a 3-carbon bridge or a 4-carbon bridge between two oxygen atoms bonded to L. One or more embodiments provide that L is a saturated C3 alkyl group, which forms a bridge between two oxygen atoms bonded to L. The term "saturated" means the 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 provide that L is a saturated C4 alkyl group, which forms a bridge between two oxygen atoms bonded to L.

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

[0022] As mentioned, M as shown 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 provide that M is zirconium. One or more embodiments provide that M is hafnium.

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

[0024] The metallocene olefin polymerization catalysts and the gas-phase diphenol polymerization catalysts prepared from the gas-phase diphenol polymerization precatalysts herein can be prepared using the reactants mentioned herein. The metallocene olefin polymerization catalysts and the gas-phase diphenol polymerization catalysts prepared from the gas-phase diphenol polymerization precatalysts herein can be prepared by a variety of methods, for example, using conventional solvents, reaction conditions, reaction times and separation procedures for preparing known catalysts such as known metallocene olefin polymerization catalysts.

[0025] One or more embodiments provide a polymerization catalyst, i.e., a gas-phase diphenol polymerization catalyst made from a gas-phase diphenol polymerization precatalyst of Formula I. The gas-phase diphenol polymerization catalyst can be prepared by contacting the gas-phase diphenol polymerization precatalyst with an activator under activation conditions to provide a gas-phase diphenol polymerization catalyst, such as an activated gas-phase diphenol polymerization precatalyst. Activation conditions are well known in the art.

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

[0027] The activator may include a Lewis acid or a non-coordinating ionic activator or an ionizing activator, or any other compound including a Lewis base, an alkyl aluminum, and / or a conventional type cocatalyst. 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 ionizing neutral or ionic compounds such as dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis(3,5-(CF3)2phenyl)borate, triphenylcarbonium tetrakis(3,5-(CF 3) 2-(2-phenyl)borate, dimethylanilinium tetra(perfluoronaphthyl)borate, triphenylcarbonium tetra(perfluoronaphthyl)borate, dimethylanilinium tetra(pentafluorophenyl)aluminate, triphenylcarbonium tetra(pentafluorophenyl)aluminate, dimethylanilinium tetra(perfluoronaphthyl)aluminate, triphenylcarbonium 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 oligomeric aluminum compounds having -Al(R)-O- subunits, wherein 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 hydrolyzing the corresponding trialkylaluminum compound. MMAO can be produced by hydrolyzing trimethylaluminum and a higher carbon trialkylaluminum (such as triisobutylaluminum). There are a variety of known methods for preparing aluminoxanes and modified aluminoxanes. Aluminoxanes can include modified methylaluminoxane type 3A ("MMAO") (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane type 3A, as discussed in U.S. Pat. No. 5,041,584). The source of MAO can be a solution having, for example, about 1 wt % to about 50 wt % MAO. Commercially available MAO solutions may include 10 wt % and 30 wt % MAO solutions available from Albemarle Corporation, of Baton Rouge, La.

[0029] One or more organoaluminum compounds, such as one or more alkylaluminum compounds, may be used in combination with aluminoxane. Examples of alkylaluminum compounds include, but are not limited to, diethylaluminum ethoxide, diethylaluminum chloride, diisobutylaluminum hydride, and combinations thereof. Examples of other alkylaluminum compounds (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-propylcyclopentadienyl)2MX2, (n-butylcyclopentadienyl)2MX2, (1-methyl, 3-n-butylcyclopentadienyl)2MX2, (pentadienyl)(1,3-dimethyl-tetrahydroindenyl)MX2, ( MX2, (methylcyclopentadienyl)(1,3-dimethyl-tetrahydroindenyl)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)alkyl or alkenyl.

[0031] A gas phase polymerization catalyst system comprising a metallocene olefin polymerization catalyst and a gas phase biphenol polymerization catalyst made from a gas phase biphenol polymerization precatalyst can be used to prepare a polymer. For example, the gas phase polymerization catalyst system and an olefin can be contacted under polymerization conditions in a gas phase polymerization reactor to prepare a polymer, such as a polyolefin polymer.

[0032] As used herein, a "polymer" has two or more identical or different polymer units derived from one or more different monomers, such as homopolymers, copolymers, terpolymers, etc. A "homopolymer" is a polymer having identical polymer units. A "copolymer" is a polymer having two or more polymer units that are different from each other. A "terpolymer" is a polymer having three polymer units that are different from each other. "Different" with respect to polymer units indicates that the polymer units differ from each other by at least one atom or isomer. Thus, as used herein, the definition of a copolymer includes terpolymers, etc. As used herein, a "polymerization process" is a process for preparing a polymer.

[0033] Embodiments provide that: polymer can be a polyolefin polymer. As used herein, "olefin", which may be referred to as "alkene", refers to a linear, 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 comprising an olefin (e.g., prepared by an olefin), the olefin present in such a polymer or copolymer is an olefin in polymerized form. For example, when it is said that the ethylene content of the copolymer is 1 wt % to 99 wt %, it is understood that the polymer units in the copolymer are derived from the ethylene in the polymerization reaction, and based on the gross weight of the polymer, the derived units are present in 1 wt % to 99 wt %. Higher α-olefins refer to α-olefins having 3 or more carbon atoms.

[0034] Polyolefins include polymers prepared from olefin monomers such as ethylene, i.e., polyethylene and straight or branched high-carbon alpha-olefin monomers containing 3 to 20 carbon atoms. Examples of high-carbon 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 polymers having at least 50% by weight of ethylene, including ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene copolymers. Other monomers that can be used include, for example, ethylenically unsaturated monomers, dienes with 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, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentane. In many embodiments, copolymers of ethylene can be produced where a comonomer having at least one alpha-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 gas phase polymerization process. In another embodiment, ethylene and / or propylene can be polymerized with at least two different comonomers, any one of which can be a diene, to prepare a terpolymer.

[0035] One or more embodiments provide that the polymer may contain 1 wt% to 100 wt% of units derived from ethylene, based on the total weight of the polymer. All individual values ​​and subranges from 1 wt% to 100 wt% are included; for example, based on the total weight of the polymer, the polymer may contain a lower limit of 1 wt%, 5 wt%, 10 wt%, or 50 wt% of units derived from ethylene to an upper limit of 100 wt%, 95 wt%, 90 wt%, 85 wt%, or 75 wt% of units derived from ethylene.

[0036] The gas phase polymerization catalyst system comprising the gas phase biphenol polymerization catalyst made of the gas phase biphenol polymerization precatalyst of formula I can contribute to providing polymer in a single gas phase reactor by a polymerization process. 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 described in detail 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 gas phase reactor via a polymerization process using a gas phase polymerization catalyst system. In some applications, it is desirable to have a high molecular weight polyethylene component and a low molecular weight polyethylene component.

[0037] Surprisingly, the gas phase polymerization catalyst system of the present disclosure comprising a gas phase diphenol polymerization catalyst made from a gas phase diphenol polymerization precatalyst of Formula I can prepare bimodal polymers comprising a high molecular weight polyethylene component having a lower molecular weight than the high molecular weight component in the polymer formed with other (non-inventive) polymerization catalysts under similar polymerization conditions, as described in detail herein. A high molecular weight polyethylene component having a lower molecular weight than the molecular weight of other high molecular weight polyethylene components is desirable in some applications.

[0038] Embodiments provide that the polymer may have an Mn (number average molecular weight) of 8,000 to 250,000. All individual values ​​and subranges of 8,000 to 250,000 are included. For example, the polymer may have an Mn of from a lower limit of 8,000; 10,000; or 12,000; to an upper limit of 250,000; 150,000; 100,000, 40,000; or 35,000. In some embodiments, the Mn may be in the range of 12,702 to 245,010.

[0039] Embodiments provide that the polymer has an Mw (weight average molecular weight) of 50,000 to 1,200,000 under B conditions and / or a molecular weight of less than 500,000 Daltons under K conditions. All individual values ​​and subranges of 50,000 to 1,200,000 μm are included; for example, the polymer may have an Mw under B conditions from a lower limit of 50,000; 100,000; or 200,000; to an upper limit of 1,200,000; 1,100,000; 1,000,000; 800,000 or 600,000. Some embodiments provide that the polymer has an Mw (weight average molecular weight) of 50,000 to 800,000 under B conditions and / or a molecular weight of less than 500,000 Daltons under K conditions. All individual values ​​and subranges of 50,000 to 800,000 are included. For example, the polymer may have a Mw of from 50,000; 100,000; or 200,000 on the lower limit; to 800,000; or 600,000 on the upper limit under B conditions. In some examples, the polymer may have a Mw of 50,000 to 500,000 under K conditions or 100,000 to 500,000 under K-conditions.

[0040] Embodiments provide that the polymer may have an Mz (z-average molecular weight) of 200,000 to 10,000,000, including all individual values ​​and subranges of 200,000 to 10,000,000; for example, the polymer may have an Mz of from a lower limit of 200,000; 700,000; or 900,000; to an upper limit of 10,000,000; 5,000,000; or 3,000,000.

[0041] Embodiments provide that the polymer may have a ratio of Mz to Mw in the range of 2.00 to 20.00, including all individual values ​​and subranges from 2.00 to 20.00; for example, the polymer may have a ratio of Mz to Mw 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 value of the Mw to Mn ratio of the polymer may be greater than 2.00, greater than 3.00, greater than 4.00, or greater than 5.00. Some embodiments provide that the Mw to Mn ratio of the polymer may be in the range of 5.00 to 75.00. All individual values ​​and subranges of 5.00 to 75.00 are included; for example, the Mw to Mn ratio of the polymer may be 5.00; 6.00; or 7.00, with an upper limit of 75.00, 60.00, or 50.00.

[0043] Embodiments provide that the ratio of the Mz to the Mw of the polymer may be less than the ratio of the Mw to the Mn of the polymer.

[0044] The embodiment provides that the polymer may have a melt index (I) in the range of 0.001 dg / 1 min to 1000 dg / 1 min. 21 dg / 1 min) as measured by ASTM D1238 (at 190°C, 21 kg load). All individual values ​​and subranges from 0.001 dg / 1 min to 1000 dg / 1 min are included.

[0045] The embodiment provides that the polymer produced using a gas phase polymerization reactor may have a melting temperature (Tm) of 110 degrees Celsius (°C) to 135 degrees Celsius. All individual values ​​and subranges from 118°C to 135°C are included; for example, the Tm of the polymer may be a lower limit of 110, 113, 118, 119, or 120°C to an upper limit of 135, 133, 132, 130, or 128°C.

[0046] The embodiment provides that the polymer may have a 3 Up to 0.970g / cm 3 Density. Including 0.890 to 0.970g / cm 3 All individual values ​​and subranges of; for example, the density of the polymer can be 0.890, 0.900, 0.910, 0.920, or 0.940 g / cm 3 The lower limit is 0.970, 0.960 or 0.950 g / cm 3 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 (used for testing solid plastics in liquids other than water, such as in liquid 2-propanol). It is expressed in grams per cubic centimeter (g / cm 3 ) as the unit to report the results.

[0047] Gel Permeation Chromatography (GPC) Test Method: Weight Average Molecular Weight Test Method: Mw, number average molecular weight (M) were determined using chromatograms obtained on a high temperature gel permeation chromatograph (HTGPC, Polymer Laboratories). n ) and M w / M n. The HTGPC was equipped with a transfer line, a differential refractive index detector (DRI), and three Polymer Laboratories PLgel 10 μm Mixed-B columns, all contained in an oven maintained at 160°C. Methods A solvent consisting of BHT-treated TCB was used with a nominal flow rate of 1.0 milliliters per minute (mL / min) and a nominal injection volume of 300 microliters (μL). The solvent was prepared by dissolving 6 grams of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent grade 1,2,4-trichlorobenzene (TCB) and filtering the resulting solution through a 0.1 micron (μm) Teflon filter to obtain the solvent. The solvent was degassed with an online degasser before entering the HTGPC instrument. The chromatographic column was calibrated with a series of monodisperse polystyrene (PS) standards. Separately, a known concentration of the test polymer dissolved in the solvent was prepared by heating a known amount of the test polymer in a known volume of solvent at 160°C and shaking continuously for 2 hours to obtain a solution. (All quantities were measured gravimetrically.) The target solution concentration c for the test polymers was 0.5 milligrams of polymer / milliliter solution (mg / mL) to 2.0 milligrams of polymer / milliliter solution, with lower concentrations c used for higher molecular weight polymers. The DRI detector was purged before running each sample. The flow rate in the apparatus was then increased to 1.0 mL / min, and the DRI detector was allowed to stabilize for 8 hours before injecting the first sample. The MW at each elution volume was calculated using the universal calibration relationship with the column calibration: The subscript "X" represents the test sample, the subscript "PS" represents the PS standard, and a PS =0.67, K 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 was calculated using the following equation: DRI Calculate the concentration c: c = K DRI I DRI / (dn / dc), where K DRIis a constant determined by calibrating the DRI, / represents division, and dn / dc is the refractive index increment of the polymer. For polyethylene, dn / dc=0.109. The polymer mass recovery is calculated by the ratio of the integrated area at the elution volume of the concentration chromatography chromatogram and the injected mass, and the injected mass is equal to the predetermined concentration multiplied by the injection loop volume. Unless otherwise stated, all molecular weights are reported in grams per mole (g / mol). Further details on the method for determining Mw, Mn, MWD are described in US 2006 / 0173123, pages 24-25, paragraphs

[0334] to

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

[0048] The polymers can be used in a variety of articles, such as films, fibers, nonwoven and / or woven fabrics, extruded articles and / or molded articles, and the like.

[0049] A gas phase polymerization catalyst system is provided, which prepares a polymer via a gas phase polymerization process, the gas phase polymerization catalyst comprising: a metallocene olefin polymerization catalyst; and a supported gas phase biphenol polymerization catalyst made from a gas phase biphenol polymerization precatalyst of formula I, as described in detail herein.

[0050] The metallocene olefin polymerization catalyst and / or the gas-phase diphenol polymerization catalyst made from the gas-phase diphenol polymerization precatalyst of Formula I and other components discussed herein such as an activator can be used together with a carrier. "Carrier" may also be referred to as "carrier" and refers to any carrier material, including porous carrier materials (such as talc), inorganic oxides and inorganic chlorides.

[0051] The metallocene olefin polymerization catalyst and / or the gas phase biphenol polymerization catalyst made of the gas phase biphenol polymerization precatalyst of formula I and other components described herein can be loaded on the same or different carriers, or one or more of the components can be used in an unloaded form. The utilization of the carrier can be achieved by any technology used in the art. One or more embodiments provide for the use of a spray drying process. The spray drying process is well known in the art. The carrier can be functionalized.

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

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

[0054] An example of a carrier is available under the trade name Cabosil TM Fumed silica obtained from TS-610, or other TS-series or TG-series supports available from Cabot Corporation. Fumed silica is typically silica having a particle size of 7 to 30 nanometers that has been treated with dimethylsilyl dichloride such that most of the surface hydroxyl groups are capped.

[0055] The support material may have a surface area ranging from about 10 to about 700 m / g, a surface area ranging from about 0.1 to about 4.0 g / cm 3 and an average particle size ranging from about 5 to about 500 μm. More preferably, the support material has a surface area ranging from about 50 to about 500 m / g and a pore volume ranging from about 0.5 to about 3.5 g / cm 3 , with an average particle size of about 10 to about 200 μm. Most preferably, the support material has a surface area in the range of about 100 to about 400 m / g and a pore volume in the range of about 0.8 to about 3.0 g / cm 3 The average particle size is about 5 to about 100 μm. The average pore size of the carrier generally has a pore size in the range of 10 to 1000 Å, preferably 50 to about 500 Å and most preferably 75 to about 350 Å.

[0056] The metallocene olefin polymerization catalyst and / or the gas phase diphenol polymerization catalyst made from the gas phase diphenol polymerization precatalyst of formula I and other components discussed herein such as an activator may be a slurry. Slurries are well known in the art. The slurry may include, for example, a metallocene olefin polymerization catalyst and / or the gas phase diphenol polymerization catalyst made from the gas phase diphenol polymerization precatalyst of formula I, an activator and a carrier.

[0057] In the slurry, the molar ratio of the metal in the activator to the metal in the metallocene olefin polymerization catalyst or the gas phase diphenol polymerization catalyst made of the gas phase diphenol 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 gas phase diphenol polymerization catalyst made of the gas phase diphenol polymerization precatalyst of formula I and the activator can be combined in the presence of toluene or another non-reactive hydrocarbon or hydrocarbon mixture. In addition to toluene, other suitable diluents can include but are not limited to ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons or any combination thereof. The support, either dry or mixed with toluene, may then be added to the mixture, or the metal-ligand complex / activator may be added to the support. The slurry may be fed to a reactor to carry out the polymerization process, and / or the slurry may be dried, such as spray dried, prior to being fed to a reactor to carry out the polymerization process.

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

[0059] One or more embodiments provide that the polymer may be formed by a gas phase polymerization system at a pressure 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 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. A stirred and / or fluidized bed gas phase polymerization system may be used.

[0060] Usually, conventional gas phase fluidized bed polymerization process can be carried out by continuously passing a material stream containing one or more olefin monomers through a fluidized bed reactor at a speed sufficient to keep a solid particle bed in a suspended state under reaction conditions and in the presence of a catalyst composition (for example, a composition comprising a gas phase polymerization catalyst system (metallocene olefin polymerization catalyst or a gas phase biphenol polymerization catalyst made of a gas phase biphenol polymerization precatalyst of formula I) and an activator. The material stream comprising unreacted monomers can be continuously recovered, compressed, cooled, optionally partially or completely condensed from the reactor, and circulated back to the reactor. The product (i.e., polymer) can be taken out from the reactor, and a substitute monomer can be added to the circulating stream. A gas inert to the catalyst composition and reactants can also be present in the gas stream. The polymerization system can include, for example, a single reactor or two or more reactors in series.

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

[0062] For the polymerization process, a polymerization catalyst (metallocene olefin polymerization catalyst and / or a gas-phase biphenol polymerization catalyst made from a gas-phase biphenol polymerization precatalyst of Formula I) can be continuously fed to the reactor. A gas inert to the polymerization catalyst (such as nitrogen or argon) can be used to bring the polymerization catalyst into the reactor bed.

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

[0064] Various aspects of the disclosure are provided as follows.

[0065] Aspect 1 provides a use of a supported gas-phase diphenol polymerization catalyst for preparing a polymer via a gas-phase polymerization process, wherein the supported gas-phase diphenol polymerization catalyst is prepared from a gas-phase diphenol polymerization precatalyst of formula I:

[0066]

[0067] Where R 5 , R 7- , R 8 and R10 Each of which is independently (C1 to C 20 ) alkyl, aryl, aralkyl, halogen or hydrogen; wherein R 4 and R 11 Each of is independently halogen or hydrogen; wherein R 2 and R 13 Each of C1 to C 20 alkyl, aryl or aralkyl or hydrogen; wherein R 15 and R 16 Each of the following is independently a 2,7-disubstituted carbazole-9-yl group or a 3,6-disubstituted carbazole-9-yl group; wherein L is a straight-chain C3 or C4 alkylene group, which forms a 3-carbon bridge or a 4-carbon bridge between the two oxygen atoms covalently bonded to L, respectively; wherein R 1 , R 3 , R 12 and R 14 Each of the following is independently (C1-C8)alkyl, halogen or hydrogen; wherein R 6 and R 9 Each of which is hydrogen or (C1-C8) alkyl; wherein each X is independently halogen, hydrogen, (C1-C 20 ) alkyl, (C7-C 20 )aralkyl, (C1-C6)alkyl-substituted (C6-C 12 )aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R C )3, where R C It is C1-C 12 A hydrocarbon; and wherein M is Zr or Hf.

[0068] Aspect 2 provides the use according to aspect 1, wherein each X is a methyl group.

[0069] Aspect 3 provides the use according to aspect 1 or 2, wherein R 1 , R 3 , R 12 and R 14 Each of them is hydrogen.

[0070] Aspect 4 provides the use according to aspect 1, 2 or 3, wherein the gas phase diphenol polymerization precatalyst of formula I is selected from the group consisting of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix), as described in detail herein.

[0071] Aspect 5 provides the use according to aspect 1, 2 or 3, wherein the gas phase diphenol polymerization precatalyst is selected from the group consisting of structures (iii) and (v), as described in detail herein.

[0072] Aspect 6 provides the use according to aspect 1, wherein the polymer formed under B conditions (H2 / C2=0.0017 and C6 / C2=0.004 at 100°C and 230 pounds per square inch (psi) ethylene) has a molecular weight (Mw) in the range of about 150,000 Daltons to about 1,200,000 Daltons; or wherein the polymer formed under K conditions (H2 / C2=0.0068 and C6 / C2=0.004 at 100°C and 230 psi) has a 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 Daltons to about 1,200,000 Daltons under B conditions and a molecular weight of less than about 500,000 under K conditions.

[0073] Aspect 7 provides a gas phase polymerization catalyst system, which prepares a polymer via a gas phase polymerization process, the gas phase polymerization catalyst comprising: a metallocene olefin polymerization catalyst; and a supported gas phase diphenol polymerization catalyst made from the gas phase diphenol polymerization precatalyst according to aspect 1. In various embodiments, part or all of the gas phase polymerization catalyst system (e.g., metallocene and / or gas phase diphenol polymerization precatalyst) is provided as a trimming solution. For example, a portion of the metallocene catalyst can be provided as a trimming solution. Alternatively, a portion of the gas phase diphenol polymerization precatalyst can be provided as a trimming solution.

[0074] Aspect 8 provides a gas phase polymerization method for preparing a polymer, comprising: polymerizing olefin monomers in a gas phase polymerization reactor in the presence of the gas phase polymerization catalyst system according to aspect 7 to prepare a polymer.

[0075] Aspect 9 provides the gas phase polymerization catalyst system according to aspect 7 or the gas phase polymerization method according to aspect 8, wherein R 15 and R 16 Each of is 3,6-di-tert-butylcarbazol-9-yl.

[0076] 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 in a single gas phase reactor via a polymerization process using the gas phase polymerization catalyst system according to aspect 7.

[0077] Example

[0078] A gas-phase diphenol polymerization catalyst made from a gas-phase diphenol polymerization precatalyst of formula (I), a gas-phase polymerization catalyst system comprising the gas-phase diphenol polymerization catalyst, and comparative gas-phase polymerization catalysts (except those made from a gas-phase polymerization precatalyst of formula (I)) were prepared as follows.

[0079] The gas phase biphenol polymerization precatalyst of structure (i) is prepared as follows. In a glove box, hafnium chloride [HfCl4] (12.07 g, 37.7 mmol; available from Strem Chemical) and toluene (300 mL; available from Fisher Scientific) and a magnetic stirring bar are loaded into a 16 oz oven-dried glass jar. The contents of the glass jar are cooled to approximately -30 degrees Celsius (°C). Methylmagnesium bromide (56.6 mL of a 2.6 M ether solution, 147 mmol; available from Millipore Sigma) is added, and the solution is stirred at -30°C for 15 minutes. The ligand of structure A (56.00 g, 35.9 mmol) is loaded into a glass jar. The ligand of structure A is prepared as described in WO2017 / 058,981, and the entire contents of WO 2017 / 058,981 are incorporated herein by reference. As the solution gradually warms to room temperature, the contents of the vial are stirred for 3 hours. The mixture was filtered and the solvent was removed from the filtrate in vacuo to obtain a grey powder (45 g, 71.0% yield). The presence of the gas phase diphenol polymerization precatalyst of structure (i) is determined by 1 H NMR analysis confirmed. 1 H NMR (400MHz, benzene-d6) δ8.19 (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).

[0080]

[0081] As used herein, "Me" refers to methyl, and "n-Oct" refers to normal C8H 17 , and "n-Pr" refers to positive C 3 H7.

[0082] The vapor phase diphenol polymerization precatalyst of structure (ii) was prepared using the same components and method as the vapor phase diphenol polymerization precatalyst of structure (i), except that zirconium chloride [ZrCl4] (15.0 g, 64.1 mmol) was used instead of hafnium chloride (99.9 g; 92.9% yield). The vapor phase diphenol polymerization precatalyst of structure (ii) was prepared by 1 H NMR analysis confirmed. 1 H NMR (400MHz, 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).

[0083]

[0084] The gas phase biphenol polymerization precatalyst of structure (iii) is prepared as follows. In a glove box, zirconium chloride [ZrCl4] (0.186 g, 0.80 mmol; available from Strem Chemical) and toluene (30 mL; available from Fisher Scientific) and a magnetic stirring bar are loaded into a 4 oz oven-dried glass jar. The contents of the glass jar are cooled to approximately -30 degrees Celsius (°C). Methylmagnesium bromide (1.12 mL of a 3.0 M ether solution, 3.34 mmol; available from Millipore Sigma) is added, and the solution is stirred at -30°C for 2 minutes. The ligand of structure B (1.00 g, 0.80 mmol) is loaded into a glass jar. The ligand of structure B is prepared as described in WO 2014 / 105411, and the entire contents of WO 2014 / 105411 are incorporated herein by reference. The contents of the vial are stirred for 2 hours as the solution gradually warms to room temperature. The mixture was filtered and the solvent was removed from the filtrate in vacuo 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 diphenol polymerization precatalyst of structure (iii) is determined by 1 H NMR analysis confirmed. 1H NMR (400MHz, benzene-d6) δ8.20(d,2H), 8.09(d,2H), 7.90(d,2H), 7.82(d,2H), 7.8 0(d,2H),7.50(dd,2H),7.37(dd,2H),7.33(d,2H),6.89(dd,2H),6.12(dd,2 H), 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).

[0085]

[0086] The gas phase biphenol polymerization precatalyst of structure (iv) is prepared as follows. 3.22M methylmagnesium bromide solution (0.57mL, 1.83mmol) was added to a suspension of ZrCl4 (102mg, 0.44mmol) in toluene (20mL) at -28°C. The solution was stirred for 2 minutes, during which a deep red color was formed. A solution of the ligand of structure C (550mg, 0.44mmol) in toluene (10mL) was then added at one time. The ligand of structure C was prepared as described in 20160108156A1, and the entire contents of 20160108156A1 are incorporated herein by reference. The solution was warmed to room temperature and stirred for a total of 4 hours. Hexane (30mL) was added, and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure. The crude solid was then absorbed in hot toluene (20mL) and filtered. The filtrate was evaporated under reduced pressure to obtain 562mg (93%) of a light yellow solid. The presence of the gas phase diphenol polymerization precatalyst of structure (iv) is due to 1 H NMR analysis confirmed. 1H NMR (400MHz, C6D6, 298K) δ8.19 (d, J=8.0Hz, 1H), 8.15 (d, J=8.0Hz, 2H), 7.73 (s, 1H), 7.66 (s, 1H), 7.60 (d, J=8.0Hz, 2H), 7.49 -7.39 (m, 4H), 7.30 (d, J=8.0Hz, 1H), 7.20 (s, 1H), d (J=8.0Hz, 1H), 7.06-7.00 (m, 3H), 6.63 (d, J=8.0Hz, 1H), 6.22 (dd, J=8.0Hz and 4.0Hz, 1H), 5.75 (td, J=8.0Hz and 4.0Hz, 1H), 3.62 (t, J=8.0Hz, 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, 12.0Hz, 3H), -0.56(s, 3H), -0.98(s, 3H).

[0087]

[0088] The gas-phase diphenol polymerization precatalyst of structure (v) is prepared as follows. To a suspension of ZrCl4 (104 mg, 0.45 mmol) in toluene (20 mL) at -28°C was added a solution of 3.22 M methylmagnesium bromide in diethyl ether (0.61 mL, 1.97 mmol). The solution was stirred for 2 minutes, during which time a deep red color was formed. A solution of the ligand of structure D (550 mg, 0.45 mmol) in toluene (10 mL) was then added in one portion. The ligand of structure D was prepared as described in US20160108156(A1), and the entire contents of US20160108156(A1) are incorporated herein by reference. The solution was allowed to warm to room temperature and stirred for a total of 4 hours. Hexane (30 mL) was added, and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure to obtain 600 mg (99%) of a light yellow solid. The presence of the gas-phase diphenol polymerization precatalyst of structure (v) is determined by 1 H NMR analysis confirmed. 1H NMR (400MHz, C6D6, 298K) δ8.15 (d, J=8.0Hz, 2H), 8.07 (dd, J=8.0and 4.0Hz, 2H), 7.71 (d, J=4.0Hz, 2H), 7.68 (d, J=4.0Hz, 2H), 7.67 (d, J=4.0Hz, 2H), 7.36 (t , J=4.0Hz, 2H), 7.33 (t, J=4.0Hz, 2H), 7.29 (d, J=4.0Hz, 2H), 7.03-7.01 (m, 3H), 6.99 (d, J=4.0Hz, 1H), 6.63 (m, 2H), 4.76 (q, J=4.0Hz, 2H), 3.91 (q, J=4.0Hz, 2H), 3.39 (q, J=4.0H z, 2H), 1.57 (q, J=12.0Hz, 6H), 1.34 (s, 18H), 1.22 (s, 30H), 0.82 (s, 18H), -0.91 (s, 6H).

[0089]

[0090] The gas-phase diphenol polymerization precatalyst of structure (vi) is prepared as follows. To a suspension of ZrCl4 (69 mg, 0.30 mmol) in toluene (20 mL) was added 3.22 M methylmagnesium bromide solution (0.40 mL, 1.30 mmol) at -28°C. The solution was stirred for 2 minutes, during which time a deep red color was formed. A solution of the ligand of structure E (513 mg, 0.30 mmol) in toluene (10 mL) was then added in one portion. The ligand of structure E was prepared as described in WO2017058981A1, and the entire contents of WO2017058981A1 are incorporated herein by reference. The solution was allowed to warm to room temperature and stirred for a total of 3 hours. Hexane (30 mL) was added, and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure to obtain 495 mg (90%) of a light yellow solid. The presence of the gas-phase diphenol polymerization precatalyst of structure (vi) is determined by 1 H NMR analysis confirmed. 1H NMR (400MHz, C6D6, 298K) δ8.27 (d, J=8.0Hz, 2H), 8.16 (d, J=8.0Hz, 2H), 8.05 (s, 2H), 7. 96 (s, 2H), 7.63 (d, J=8.0Hz, 2H), 7.56 (d, J=8.0Hz, 2H), 6.92 (d, J=4.0Hz, 2H), 6.79 (d, J =4.0Hz, 2H), 6.77 (d, J = 4.0Hz, 2H), 6.13 (d, J = 4.0Hz, 1H), 6.11 (d, J = 4.0Hz, 1H), 3.54 ( q, J=4.0Hz, 2H), 3.30 (q, J=4.0Hz, 2H), 2.13 (s, 6H), 1.66-0.89 (m, 130H), -0.42 (s, 6H).

[0091]

[0092]

[0093] The gas phase diphenol polymerization precatalyst of structure (vii) was prepared as follows.

[0094]

[0095] Synthesis of 1-(4-bromobutoxy)-4-fluoro-2-iodobenzene: 4-fluoro-2-iodophenol (3.20 g, 13.45 mmol, disclosed in US2015 / 0291713A1), anhydrous potassium carbonate (3.79 g, 27.45 mmol), 1,4-dibromobutane (28 mL, 234.47 mmol) and acetone (92 mL) were charged into a three-necked round-bottom flask equipped with a stirring bar, a septum, a condenser and a nitrogen inlet. The mixture was stirred at reflux for 3 hours and then cooled to room temperature. The mixture was filtered, the solid was washed with acetone, and the filtrate was concentrated by rotary evaporation to remove acetone. In order to remove excess 1,4-dibromobutane, the remaining yellow solution was heated at 60 ° C and distilled under high vacuum using a short path distillation head while slowly increasing the temperature to obtain 4.45 g (88.8%) of the product as a light brown oil.

[0096] 1 H-NMR (400MHz, CDCl3) δ7.48 (dd, J=7.6, 3.0Hz, 1H), 7.00 (ddd, J=9.0, 7.8, 3.0Hz, 1H), 6.71 (dd, J= 9.0, 4.6Hz, 1H), 3.99 (t, J=5.9Hz, 2H), 3.53 (t, J=6.6Hz, 2H), 2.18-2.09 (m, 3H), 2.02-1.94 (m, 2H).13 C-NMR (101MHz, CDCl3) δ156.64 (d, J=244.0Hz), 153.93 (d, J=2.2Hz), 125.94 (d, J=25.0Hz), 115.48 (d, J=22.7Hz), 112.05 (d, J=8.2Hz), 85.94 (d, J=8.3Hz), 68.74, 33.54, 29.42, 27.63. 19 F-NMR (376MHz, CDCl3) δ-122.33 (td, J=7.9, 4.8Hz).

[0097]

[0098] Synthesis of 5-fluoro-2-(2-(4-fluoro-2-iodophenoxy)ethoxy)-1-iodo-3-methylbenzene: 1-(4-bromobutoxy)-4-fluoro-2-iodobenzene (3.66 g, 9.81 mmol), 4-fluoro-2-iodo-6-methylphenol (2.47 g, 9.82 mmol, preparation disclosed in US2015 / 0291713A1), anhydrous potassium carbonate (2.87 g, 20.76 mmol) and acetone (66 mL) were loaded into a three-necked round-bottom flask equipped with a stirring bar, a septum, a condenser and a nitrogen inlet. The mixture was stirred at reflux for 5.5 hours and then cooled to room temperature. The mixture was filtered, the solid was washed with acetone, and the filtrate was concentrated by rotary evaporation to give a crude dark red oil (5.30 g). The oil is dissolved in a minimum amount of hexane and purified by flash column chromatography (ISCO, 330g silica gel, 0-5% ethyl acetate / hexane). The fractions containing the product are combined and concentrated by rotary evaporation to give a yellow oil. In order to remove trace amounts of ethyl acetate, the oil is dissolved in dichloromethane and concentrated by rotary evaporation to give a yellow oil (repeated twice). The oil is dried under high vacuum to give 4.33g (81.2%) of the product in the form of a yellow oil.

[0099] 1 H NMR (400MHz, CDCl3) δ7.50 (dd, J=7.6, 3.0Hz, 1H), 7.31 (ddd, J=7.5, 3.0, 0.7Hz, 1H), 7.01 (ddd, J=9.0, 7.8, 3.0Hz, 1H) , 6.91-6.85 (m, 1H), 6.76 (dd, J=9.0, 4.6Hz, 1H), 4.12-4.05 (m, 2H), 3.95-3.88 (m, 2H), 2.32 (s, 2H), 2.14-2.09 (m, 4H). 13C NMR (101MHz, CDCl3) δ158.71 (d, J=168.7Hz), 156.27 (d, J=165.2Hz), 154.13 (d, J=1.9H z), 153.41 (d, J = 1.5Hz), 133.04 (d, J = 8.3Hz), 125.95 (d, J = 24.9Hz), 123.28 (d, J = 24.8 Hz), 117.84 (d, J=22.2Hz), 115.51 (d, J=22.6Hz), 112.27 (d, J=8.1Hz), 91.35 (d, J=9.5 Hz), 86.07 (d, J=8.7Hz), 72.45 (d, J=1.4Hz), 69.61, 26.91, 26.00, 17.30 (d, J=1.5Hz). 19 F NMR (376MHz, CDCl3) δ -118.22 (t, J=8.1Hz), -122.40 (td, J=7.6, 4.5Hz).

[0100]

[0101] The reaction was set up in a glove box under a nitrogen atmosphere. Zirconium tetrachloride (0.037 g, 0.16 mmol) and toluene (10 mL) were charged into a glass jar. The slurry mixture was cooled to -25°C in a glove box freezer. 3.0 M methylmagnesium bromide (0.25 mL, 0.75 mmol) in ether was added to the stirred cold slurry mixture. The mixture was stirred vigorously for about 4 minutes. The solid was dissolved in the solution and it turned brown. A ligand of structure F (0.20 g, 0.16 mmol) was added to the mixture in the form of a solid. The resulting mixture was stirred at room temperature for 5 hours. Hexane (10 mL) was then added to the mixture and filtered. The solution was concentrated under vacuum to give 0.25 g (complete conversion) of the product in the form of a light yellow solid. The excess mass was attributed to the presence of residual toluene in combination with complete conversion observed in the proton NMR. The presence of a gas phase diphenol polymerization precatalyst of structure (vii) is indicated by 1 H NMR analysis confirmed. 1H NMR (400MHz, benzene-d6) δ8.18 (d, J=8.2Hz, 1H), 8.15 (d, J=8.2Hz, 1H), 8.08 (d, J=8 .3Hz, 1H), 7.88 (d, J=1.7Hz, 1H), 7.80 (d, J=2.0Hz, 2H), 7.72 (d, J=1.6Hz, 2H), 7.69 (d, J=2.5Hz, 1H), 7.48-7.40 (m, 2H), 7.40-7.34 (m, 3H), 7.23 (d, J=2.5Hz, 1H), 6.99-6.90 (m, 2H), 6.55 (ddd, J=9.0, 7.1, 3.2Hz, 1H), 6.14 (dd, J=8.5, 3.2 Hz, 1H), 5.15 (dd, J=9.1, 4.9Hz, 1H), 4.44 (t, J=11.7Hz, 1H), 3.91-3.70 (m, 2H) , 3.37 (dd, J=11.0, 7.6Hz, 1H), 1.78 (d, J=14.5Hz, 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), 1.1 3(s, 3H), 0.89(s, 9H), 0.83(s, 3H), 0.81(s, 10H), -0.70(s, 3H), -1.03(s, 3H).

[0102]

[0103] The gas phase diphenol polymerization precatalyst of structure (viii) is prepared as described in US 9000108 B2, and the entire contents of US 9000108 B2 are incorporated herein by reference.

[0104]

[0105] The gas phase diphenol polymerization precatalyst of structure (ix) was prepared according to the procedure described in US 9029487 B2, and the entire contents of US 9029487 B2 are incorporated herein by reference.

[0106]

[0107] Comparative gas phase polymerization catalysts (except those made from gas phase polymerization precatalysts of formula (I)) are prepared as follows. The comparative catalyst may contain a branched or substituted bridge. For example, as shown in structures (x) and (xi), the comparative catalyst may contain a branched or substituted bridge formed between two oxygen atoms.

[0108] A comparative polymerization precatalyst of structure (x) was prepared according to the procedure described in US20170137550A1, and the entire contents of US20170137550A1 are incorporated herein by reference.

[0109]

[0110] A comparative polymerization precatalyst of structure (xi) was prepared according to the procedure described in US20170137550A1, and the entire contents of US20170137550A1 are incorporated herein by reference.

[0111]

[0112] In various embodiments, gas phase diphenol polymerization catalysts made from procatalysts of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), and (ix) can be used to prepare polymers.

[0113] Example 1 (EX1), an activated and supported vapor phase diphenol polymerization catalyst of formula I was prepared as follows. In a nitrogen purged glove box, an oven dried glass bottle was charged with a slurry of 2.65 grams (g) of treated fumed silica (CABOSIL TS-610; available from WR Grace) in 75 g of toluene (available from Aldrich) and a stir bar and stirred until fully dispersed. 22 g of 10 wt % methylaluminoxane (MAO) (available from WR Grace in the form of 10 wt % in toluene) was added to the bottle to prepare a mixture. The mixture was magnetically stirred for 15 minutes, then the vapor phase diphenol polymerization precatalyst of structure i (0.303 g) was added and the mixture was stirred for 30 minutes to 60 minutes. The mixture was spray dried using a Buchi micro spray dryer B-290 with the following parameters to obtain the dried, supported and activated gas phase diphenol polymerization catalyst of Example 1: set temperature -185°C, outlet temperature -100°C (minimum), aspirator -95 and pump speed -150rpm.

[0114] Example 2 (EX2) was prepared identically to Example 1, except that the activated and supported gas phase diphenol polymerization catalyst of Example 2 was used, as indicated in Table 1.

[0115] Example 3 (EX3) was prepared identically to Example 1, except that the activated and supported gas phase diphenol polymerization catalyst of Example 3 was used, as indicated in Table 1.

[0116] Example 4 (EX4) was prepared identically to Example 1, except that the activated and supported gas phase diphenol polymerization catalyst of Example 4 was used, as indicated in Table 1.

[0117] Example 5 (EX5) was prepared identically to Example 1, except that the activated and supported gas phase diphenol polymerization catalyst of Example 5 was used, as indicated in Table 1.

[0118] Example 6 (EX6) was prepared identically to Example 1, except that the activated and supported gas phase diphenol polymerization catalyst of Example 6 was used, as indicated in Table 1.

[0119] Example 7 (EX7) was prepared identically to Example 1, except that the activated and supported gas phase diphenol polymerization catalyst of Example 7 was used under the conditions as indicated in Table 1.

[0120] Example 8 (EX8) was prepared identically to Example 1, except that the activated and supported gas phase diphenol polymerization catalyst of Example 8 was used, as indicated in Table 1.

[0121] Example 9 (EX9) was prepared identically to Example 1, except that the activated and supported gas phase diphenol polymerization catalyst of Example 9 was used, as indicated in Table 1.

[0122] Comparative Example 1 (CE1) was prepared identically to Example 1, except that the catalyst of Comparative Example 1 was used, as indicated in Table 1.

[0123] Comparative Example 2 (CE2) was prepared identically to CE1, except that the catalyst of Comparative Example 2 was prepared under the conditions as indicated in Table 1.

[0124] Comparative Example 3 (CE3) was prepared identically to Example 1, except that the catalyst of Comparative Example 1 was used, as indicated in Table 1.

[0125] Comparative Example 4 (CE4) was prepared identically to CE3, except that the catalyst of Comparative Example 4 was prepared under the conditions as indicated in Table 1.

[0126] The ethylene / 1-hexene copolymerization of each of the single catalysts of EX1-9 and CE1 was carried out in the gas phase in a 2L semi-batch autoclave polymerization reactor equipped with a mechanical stirrer as follows. The reactor was first dried for 1 hour, loaded with 200g 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 scavenger under nitrogen pressure. After adding SMAO, the reactor was sealed and the components were stirred. Hydrogen (H2 preloaded, as indicated below for each condition) and hexene (C6 / C2 ratio, as indicated below for each condition) were then charged into the reactor and then pressurized with ethylene (230psi). Once the system reached a steady state, the corresponding activated catalyst of the type and amount determined as Table 1 and Table 2 for each of EX1-9 and CE1 was charged into the reactor at 80°C to start polymerization. The reactor temperature was brought to 90°C or 100°C and maintained at that temperature throughout the 1 hour run. The runs were conducted under conditions B or K, as detailed below in Table 1. At the end of the run, the reactor was cooled, vented and opened. The resulting product mixture was washed with water and methanol and then dried. The results for EX1-9 and CE1 are shown in Tables 1 and 2.

[0127] In various embodiments, gas phase diphenol polymerization catalysts made from precatalysts of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix) can be used in the gas phase polymerization catalyst system of the present invention to prepare a high molecular weight polyethylene component in a multimodal (e.g., bimodal) polyethylene composition.

[0128] Mn (number average molecular weight) and Mw (weight average molecular weight), z average molecular weight (Mz) are determined by gel permeation chromatography (GPC), as known in the art.

[0129] The yield (kg polymer / kg catalyst) was determined as the ratio of the amount of polymer produced to the amount of catalyst and activator added to the reactor.

[0130] The melting temperature (ie, Tm) can be determined via 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 used.

[0131] The comonomer content (ie, 1-hexene) incorporated into the polymer (wt %) was determined by fast FT-IR spectroscopy of the dissolved polymer in the GPC measurement.

[0132] B-conditions were as follows: Temperature = 100°C; Ethylene = 230 psi; H2 / C2 = 0.0017; C6 / C2 = 0.004.

[0133] K-conditions are as follows: temperature = 100°C; ethylene = 230 psi; H2 / C2 = 0.0068; C6 / C2 = 0.004.

[0134] Table 1

[0135] Pre-catalyst structure condition Catalyst charge (mg) Catalyst production (gPE / gcat / hr) 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 EX6 vi B 10.3 6155 EX7 vii K 6.2 2967 EX8 viii B 5.2 15846 EX9 ix B 12 1754 CE1 x B 15.1 11053 CE2 x K 14.3 4112 CE3 xi B 15.3 2379 CE4 xi K 15.5 3226

[0136] Table 2

[0137]

[0138]

[0139] Ultra-high molecular weight (UHMW) refers to a single-chain polyethylene polymer having a polyethylene equivalent molecular weight of 2,000,000 Daltons or greater, as measured by conventional GPC. That is, in Table 2, "UHMW" is listed for those polymers having ultra-high molecular weights that can be accurately measured by the GPC test method (e.g., due to poor solubility of the polymer, line plugging, poor mass recovery, or other analytical problems commonly encountered with polyethylene polymers having molecular weights greater than two million Daltons).

[0140] As detailed in Tables 1 and 2, EX1-9 provides the use of a supported gas phase biphenol polymerization catalyst to prepare a polymer via a gas phase polymerization process, wherein the supported gas phase biphenol polymerization catalyst is made from a gas phase biphenol polymerization precatalyst of Formula I.

[0141] The resulting polymers of EX1-9 have improved (i.e., lower) molecular weights compared to polymers made from comparative catalysts under similar conditions. For example, each of EX1-9 provides polymers having molecular weights in the range of 150,000 Daltons to 1,200,000 Daltons under B conditions and / or values ​​less than 500,000 Daltons under K conditions, which may be desirable for certain applications. For example, each of the supported gas-phase diphenol polymerization catalysts of EX1-9 can be used with a metallocene olefin polymerization catalyst to prepare a gas-phase polymerization catalyst system that can be used in a single gas-phase polymerization reactor to prepare a multimodal (e.g., bimodal) polymer.

[0142] The supported gas phase biphenol polymerization catalyst of Formula I can be used to prepare polymers via a gas phase polymerization process having improved comonomer incorporation relative to the amount of comonomer incorporation carried out in a polymer prepared via a liquid phase polymerization process using a biphenol polymerization catalyst of Formula I (e.g., the same supported gas phase biphenol polymerization catalyst of Formula I). ​​The supported gas phase biphenol polymerization catalyst of Formula I can be used to prepare polymers via a gas phase polymerization process having improved comonomer incorporation relative to the amount of comonomer incorporation in a polymer made from a comparative gas phase catalyst under similar gas phase conditions.

Claims

1. A use of a supported gas-phase diphenol polymerization catalyst for preparing a polymer via a gas-phase polymerization process, wherein the supported gas-phase diphenol polymerization catalyst is prepared from a gas-phase diphenol polymerization precatalyst of formula I: Where R 5 , R 7 , R 8 and R 10 Each of which is independently (C1 to C 20 )alkyl, halogen or hydrogen; Where R 4 and R 11 Each of is independently halogen or hydrogen; Where R 2 and R 13 Each of which is independently (C1 to C 20 )alkyl or hydrogen; Where R 15 and R 16 Each of is independently a 2,7-disubstituted carbazole-9-yl group or a 3,6-disubstituted carbazole-9-yl group; wherein L is a straight-chain C3 alkylene group which forms a 3-carbon bridge between the two oxygen atoms covalently bonded to L; Where R 1 , R 3 , R 12 and R 14 Each of is independently hydrogen; Where R 6 and R 9 Each of them is hydrogen; Wherein each X is independently halogen, hydrogen or (C1-C 20 ) alkyl; and Wherein M is Zr or Hf.

2. The method according to claim 1, wherein each X is a methyl group.

3. The use according to claim 1, wherein the gas phase diphenol polymerization precatalyst is selected from the group consisting of structures (iii) and (v). as well as 4. The use according to claim 1, wherein the polymer formed under B conditions of H2 / C2=0.0017 and C6 / C2=0.004 at 100°C and 230 pounds per square inch (psi) ethylene has a molecular weight Mw in the range of about 150,000 Daltons to about 1,200,000 Daltons; or wherein the polymer formed under K conditions of H2 / C2=0.0068 and C6 / C2=0.004 at 100°C and 230 psi has a Mw of less than about 500,000 Daltons.

5. A use of a supported gas-phase diphenol polymerization catalyst for preparing a polymer via a gas-phase polymerization process, wherein the supported gas-phase diphenol polymerization catalyst is made from a gas-phase diphenol polymerization precatalyst, and the gas-phase diphenol polymerization precatalyst is selected from structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix): as well as 6. A gas phase polymerization catalyst system for preparing a polymer via a gas phase polymerization process, the gas phase polymerization catalyst comprising: Metallocene olefin polymerization catalysts; and The supported gas-phase diphenol polymerization catalyst is prepared from the gas-phase diphenol polymerization precatalyst according to claim 1 or 5.

7. The gas phase polymerization catalyst system according to claim 6, wherein R 15 and R 16 Each of is 3,6-di-tert-butylcarbazol-9-yl.

8. A gas phase polymerization method for preparing a polymer, the method comprising: Olefin monomers are polymerized in a gas phase polymerization reactor in the presence of the gas phase polymerization catalyst system according to claim 6 to prepare the polymer.

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