Titanium Biphenyl Phenol Polymerization Catalyst

Abstract

Embodiments of the present disclosure relate to a titanium biphenylphenol polymerization precatalyst of formula (I):

Description

Technical Field

[0001] Embodiments of the present disclosure relate to a titanium biphenylphenol polymerization catalyst, and more specifically, to a titanium biphenylphenol polymerization catalyst of Formula I.

Background Art

[0002] Polymers can be used in many products, particularly films, fibers, nonwovens and / or woven fabrics, extruded articles, and / or molded articles. Polymers can be formed by reacting one or more monomers in a polymerization reaction in the presence of a polymerization catalyst.

Summary of the Invention

[0003] The present disclosure provides various embodiments comprising a titanium biphenylphenol prepolymerization catalyst of Formula I,

Chemical Formula

[0004] wherein R 7 and R 8 each independently is C 1 to C 20 alkyl, aryl, aralkyl, or hydrogen, R 5 and R 10 each independently is C 1 to C 20 alkyl, aryl, aralkyl, halide, or hydrogen, each R 2 and R 13 independently is C 1 to C 20 alkyl, aryl, aralkyl, or hydrogen, R 15 and R 16 each is 2,7-disubstituted carbazol-9-yl or 3,6-disubstituted-carbazol-9-yl, L is C 2 to C 4 alkylene forming a 2-carbon bridge, 3-carbon bridge, or 4-carbon bridge respectively between two oxygen atoms to which L is covalently bonded, R 1, R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 Each of, R, 3 , R, 4 , R, 6 , R, 9 , R, 11 , R, 12 , and R, 14 is independently a halide or hydrogen, each X is independently a hydrocarbyl, halide, pseudohalide, hydroxy group, alkoxy group, phenoxy group, aryloxy group, or hydrogen, and at least one X is not a hydrocarbyl. As used herein, a pre-catalyst is a catalyst compound before being exposed to an activator.

[0005] A method for preparing a titanium biphenylphenol polymerization catalyst, the method comprising activating a titanium biphenylphenol polymerization pre-catalyst of formula I by contacting the titanium biphenylphenol polymerization pre-catalyst of formula I with an activator under activation conditions, thereby preparing a titanium biphenylphenol polymerization catalyst.

[0006] A titanium biphenylphenol polymerization catalyst,

[0007] A method for preparing polyethylene, the method comprising polymerizing an olefin monomer in a single gas-phase polymerization reactor in the presence of a titanium biphenylphenol polymerization catalyst as described herein to prepare a polyethylene composition.

DETAILED DESCRIPTION OF THE INVENTION

[0008] The titanium biphenylphenol polymerization pre-catalyst of the present specification can be represented by formula I.

CHEMICAL FORMULA

[0009] Surprisingly, the polymerization catalyst prepared using the titanium biphenylphenol polymerization precursor of the present disclosure can produce a polymer of lower molecular weight compared to the polymers prepared with other (non-inventive) polymerization catalysts under similar polymerization conditions, as detailed herein. In some applications, a polymer of lower molecular weight is desirable.

[0010] In addition, surprisingly, the titanium biphenylphenol polymerization catalyst of the present disclosure can have a lower catalyst productivity than other polymerization catalysts under similar polymerization conditions, as detailed herein. In some processes, a lower catalyst productivity is desirable.

[0011] Furthermore, surprisingly, the titanium biphenyl phenol polymerization catalyst of the present disclosure can produce polymers that incorporate less comonomer compared to polymers made with other polymerization catalysts under similar polymerization conditions. In some applications, it is desirable to incorporate less comonomer.

[0012] Furthermore, surprisingly, the titanium biphenyl phenol polymerization catalyst of the present disclosure can provide improved reactor operability, as detailed herein.

[0013] As described above, each of R as shown in Formula I 7 and R 8 can each independently be C 1 ~C 20 alkyl, aryl, aralkyl, or hydrogen. In one or more embodiments, each of R 7 and R 8 is hydrogen, provided that. In one or more embodiments, each of R 7 and R 8 is C 1 alkyl, for example, methyl, provided that.

[0014] As used herein, "alkyl" includes linear, branched, and cyclic paraffin groups lacking one hydrogen. Thus, for example, the CH 3 group ("methyl") and the CH 3 CH 2 group ("ethyl") are examples of alkyl.

[0015] As used herein, "aryl" includes phenyl, naphthyl, pyridyl, and other radicals whose molecules have a ring structure characteristic of benzene, naphthylene, phenanthrene, anthracene, etc. It is understood that "aryl" may be C 6 ~C 20 aryl. For example, the C 6 H 5 -aromatic structure is "phenyl", and -C 6 H 4- The aromatic structure is "phenylene".

[0016] As used herein, "aralkyl", which may also be referred to as "arylalkyl", is an alkyl having an aryl pendant therefrom. An "aralkyl" group can be a C 7 ~C 20 aralkyl group. "Alkylaryl" is an aryl having one or more alkyl pendants therefrom.

[0017] As described above, each of R 5 and R 10 in Formula I can independently be C 1 ~C 20 alkyl, aryl, aralkyl, halide, or hydrogen. As used herein, "hydrocarbyl" includes aliphatic, cyclic, olefinic, acetylenic, and aromatic groups (i.e., hydrocarbon groups) containing hydrogen and carbon lacking one hydrogen. In one or more embodiments, each of R 5 and R10 is a dialkyl- or trialkyl-substituted silyl. In one or more embodiments, each of R 5 and R 10 is octyldimethylsilyl. In one or more embodiments, each of R 5 and R 10 is a halide. In one or more embodiments, each of R 5 and R 10 is fluorine.

[0018] As described above, each of R 2 and R 13 in Formula I can independently be C 1 ~C 20 alkyl, aryl, aralkyl, or hydrogen. In one or more embodiments, each of R 2 and R 13 is 1,1-dimethylethyl.

[0019] As described above, R as shown in Formula I 15 and R 16 each can independently be 2,7-disubstituted carbazol-9-yl or 3,6-disubstituted carbazol-9-yl. As used herein, "disubstituted carbazol-9-yl" refers to a polycyclic aromatic hydrocarbon containing two 6-membered benzene rings fused to either side of a 5-membered nitrogen-containing ring, where the two 6-membered benzene rings are each substituted and nitrogen (at the 9-position of the carbazole ring) is the point of attachment. For example, in one or more embodiments, each of R 15 and R 16 is 2,7-di-t-butylcarbazol-9-yl or 3,6-di-t-butylcarbazol-9-yl, respectively, provided that

[0020] As described above, as shown in Formula I, L is C 2 ~C 4 alkylene that forms a 2-carbon bridge, a 3-carbon bridge, or a 4-carbon bridge, respectively, between two oxygen atoms to which L is covalently bonded. In one or more embodiments, L is saturated C 3 alkyl, provided that

[0021] As described above, each of R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 as shown in Formula I can independently be a halide or hydrogen. In one or more embodiments, each of R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 is hydrogen, provided that

[0022] As described above, each X as shown in Formula I can independently be a hydrocarbyl, halide, pseudohalide, hydroxy group, alkoxy group, phenoxy group, aryloxy group, or hydrogen, with at least one X being independently not a hydrocarbyl. In one or more embodiments, each X is chlorine. As used herein, a pseudohalide refers to a compound that is not a halide but is a halide analog in terms of its charge and reactivity. Examples of pseudohalides include azide, cyano, isocyano, sulfanide, thiocyano, triflate, tosyl, and tosylate.

[0023] As shown in Formula I, the central atom is titanium (Ti).

[0024] Each of the R groups (R 1 ~R 16 ) and X as described herein can independently be substituted or unsubstituted. As used herein, "substituted" indicates that the group following the term bears at least one moiety in place of one or more hydrogens at any position, and the moiety is selected from a halogen radical, a hydroxyl group, a carbonyl group, a carboxyl group, an amine group, a phosphine group, an alkoxy group, a phenyl group, a naphthyl group, a C 1 ~C 20 alkyl group, a C 2 ~C 10 alkenyl group, and combinations thereof. "Disubstituted" refers to the presence of two or more substituents at any position, and the moiety is selected from a halogen radical, a hydroxyl group, a carbonyl group, a carboxyl group, an amine group, a phosphine group, an alkoxy group, a phenyl group, a naphthyl, a C 1 ~C 20 alkyl group, a C 2 ~C 10 alkenyl group, and combinations thereof.

[0025] The titanium biphenylphenol polymerization catalyst of formula I can be prepared using the reactants described herein. The titanium biphenylphenol polymerization catalyst of formula I can be prepared, for example, by some of the processes used to prepare known catalysts, such as conventional solvents, reaction conditions, reaction times, and isolation procedures.

[0026] One or more embodiments provide a polymerization catalyst. The polymerization catalyst can be prepared by contacting a titanium biphenylphenol polymerization precatalyst of formula i, ii, iii, iv, and / or v, as described herein, with an activator under activation conditions as described herein, and an activated titanium biphenylphenol polymerization catalyst can be provided. Activation conditions are well known in the art.

[0027] As used herein, "activator" refers to any compound or combination of compounds, supported or unsupported, that can activate a complex or catalyst component, for example, by generating a cationic species of the catalyst component. For example, this can include the removal of at least one leaving group from the metal center of the complex / catalyst component, for example, from the metal complex of formula I, such as the "X" group described herein. The activator can also be referred to as a "cocatalyst". As used herein, "leaving group" refers to one or more chemical moieties that are bonded to a metal atom and can be removed by an activator and thus can generate a species active for olefin polymerization.

[0028] The activator can include a Lewis acid or a non-coordinating ionic activator or an ionizing activator, or a Lewis base, an aluminum alkyl, and / or any other compound including a conventional cocatalyst. In addition to the above-mentioned methylaluminoxane (「MAO」) and modified methylaluminoxane (「MMAO」), exemplary activators include, but are not limited to, an aluminoxane or a modified aluminoxane, and / or an ionizing compound, neutral or ionic, such as dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis(3,5-(CF 3 ) 2 phenyl)borate, triphenylcarbenium tetrakis(3,5-(CF 3 ) 2 phenyl)borate, dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, dimethylanilinium tetrakis(pentafluoronaphthyl)aluminate, triphenylcarbenium tetrakis(pentafluoronaphthyl)aluminate, dimethylanilinium tetrakis(perfluoronaphthyl)aluminate, triphenylcarbenium tetrakis(perfluoronaphthyl)aluminate, tris(perfluorophenyl)boron, tris(perfluoronaphthyl)boron, tris(perfluorophenyl)aluminum, tris(perfluoronaphthyl)aluminum, or any combination thereof.

[0029] Aluminoxane can be described as an oligomeric aluminum compound having -Al(R)-O- subunits (wherein R is an alkyl group). Examples of aluminoxane include, but are not limited to, methylaluminoxane ("MAO"), modified methylaluminoxane ("MMAO"), ethylaluminoxane, isobutylaluminoxane, or combinations thereof. Aluminoxane can be produced by hydrolysis of each trialkylaluminum compound. MMAO can be produced by hydrolysis of trimethylaluminum and higher trialkylaluminums such as triisobutylaluminum. There are various known methods for preparing aluminoxane and modified aluminoxane. Aluminoxane can include modified methylaluminoxane ("MMAO") type 3A (the trade name of modified methylaluminoxane type 3A considered in U.S. Patent No. 5,041,584 and commercially available from Akzo Chemicals, Inc.). The MAO source can be, for example, a solution having from about 1 wt% to about 50 wt% MAO. Commercially available MAO solutions can include 10 wt% and 30 wt% MAO solutions available from Albemarle Corporation (Baton Rouge, La).

[0030] One or more organoaluminum compounds such as one or more alkylaluminum compounds can 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, such as trialkylaluminum compounds, include, but are not limited to, trimethylaluminum, triethylaluminum ("TEAL"), triisobutylaluminum ("TiBAl"), tri-n-hexylaluminum, tri-n-octylaluminum, tripropylaluminum, tributylaluminum, and combinations thereof.

[0031] A polymer can be produced using a titanium biphenylphenol polymerization catalyst prepared from a titanium biphenylphenol prepolymer of formula I. For example, the titanium biphenylphenol polymerization catalyst can be contacted with an olefin under polymerization conditions for producing a polymer, such as a polyolefin polymer.

[0032] As used herein, "polymer" has two or more same or different polymer units derived from one or more different monomers, such as homopolymers, copolymers, terpolymers, etc. A "homopolymer" is a polymer having the same polymer units. A "copolymer" is a polymer having two or more different polymer units from each other. A "terpolymer" is a polymer having three different polymer units from each other. When referring to polymer units, "different" indicates that the polymer units differ from each other by at least one atom or are isomerically different. Thus, the definition of copolymer used herein includes terpolymers and the like. As used herein, "polymerization process" is a process used to form a polymer.

[0033] Embodiments are conditional on the polymer being a polyolefin polymer. As used herein, "olefin", which may be referred to as "alkene", refers to a straight-chain, branched, or cyclic compound containing carbon and hydrogen and having at least one double bond. As used herein, when a polymer or copolymer is said to contain an olefin (e.g., made from an olefin), the olefin present in such polymer or copolymer is in a polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 75 wt% to 85 wt%, it is understood that the polymer units in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present at 75 wt% to 85 wt% based on the total weight of the polymer. Higher α-olefins mean α-olefins having three or more carbon atoms.

[0034] Examples of polyolefins include polymers made from olefin monomers such as ethylene, i.e., polyethylene, and linear or branched higher α-olefin monomers containing 3 to 20 carbon atoms. Examples of higher α-olefin monomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 3,5,5-trimethyl-1-hexene. Examples of polyolefins include, in particular, ethylene-based polymers having at least 50% by weight of ethylene, such as ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene copolymers. Other olefins that can be used include, for example, ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cyclic olefins. Examples of monomers can include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentene. In many embodiments, copolymers of ethylene are produced, where ethylene and a comonomer having at least one α-olefin having 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, and most preferably 4 to 8 carbon atoms can be polymerized by a solution process. In another embodiment, ethylene and / or propylene can be polymerized with at least two different comonomers to produce a terpolymer, optionally where one of them can be a diene.

[0035] One or more embodiments are conditional on the polymer being able to contain from 1 to 100% by weight of units derived from ethylene, based on the total weight of the polymer. All individual values and subranges from 1 to 100% by weight are included, e.g., the polymer can contain from 1, 5, 10, 30, 40, 50, 60, or 70% by weight of units derived from ethylene at the lower limit to 100, 99, 95, 90, or 85% by weight of units derived from ethylene at the upper limit, based on the total weight of the polymer.

[0036] As described above, surprisingly, the polymerization catalyst prepared from the titanium biphenylphenol polymerization pre-catalyst of formula I can have a desirable (lower) productivity compared to the polymers prepared with other polymerization catalysts under similar polymerization conditions. For example, the polymerization catalyst prepared from the titanium biphenylphenol polymerization pre-catalyst of formula I has a productivity (gPE / g catalyst / hour) in the range of 35 to 5,000,000 gPE / g catalyst / hour. All individual values and sub-ranges of 35 to 5,000,000 gPE / g catalyst + activator / hour are included. For example, the productivity can be in the range of 35 to 5,000,000, 35 to 100,000, 35 to 50,000, 35 to 10,000, 35 to 5000, 35 to 3500, 500 to 3200, or 500 to 2300 gPE / g catalyst / hour when compared to the polymers prepared with other polymerization catalysts when both polymerizations occur at the same polymerization temperature and conditions such as the same hydrogen concentration and / or the same comonomer to monomer ratio. Without wishing to be bound by theory, the lower productivity is considered desirable as it can reduce reactor fouling due to thermal excursions, reduce catalyst degradation, and / or otherwise improve operability compared to catalysts that are highly productive under similar conditions and cause operability problems in gas phase polymerization reactors.

[0037] Furthermore, as described above, surprisingly, the titanium biphenylphenol polymerization pre-catalyst of Formula I can assist in providing a polymer with improved, i.e., lower molecular weight, compared to polymers made with other polymerization catalysts under similar polymerization conditions. For example, the titanium biphenylphenol polymerization catalyst of the present disclosure can assist in providing a polymer with a reduced molecular weight compared to polymers made with other polymerization catalysts when both polymerizations occur at the same polymerization temperature and conditions such as the same hydrogen concentration and / or the same comonomer-to-monomer ratio. Embodiments are conditioned on the polymer having an Mw (weight average molecular weight) of from 60,000 to 350,000. All individual values and subranges from 60,000 to 350,000 are included, for example, the polymer can have an Mw of from a lower limit of 60,000, 100,000, 102,000, or 105,000 to an upper limit of 350,000, 336,000, 286,000, 273,000, 203,000, or 110,000. Mw can be determined by GPC as described below. Without wishing to be bound by theory, low molecular weight polymers are thought to be easier to process than high molecular weight polymers because the viscosity of the melt phase is lower.

[0038] Embodiments are conditioned on the polymer having a melt index (I 2 ) measured by D1238 (at 190 °C, 2.16 kg load) in the range of 0.001 g / 10 min to 1000 g / 10 min. All individual values and subranges from 0.001 g / 10 min to 1000 g / 10 min are included. For example, the polymer can have a melt index in the range of 0.001 g / 10 min to 1000 g / 10 or 500 g / 10 min, 0.1 g / 10 min to 100 g / 10 min, or 0.005 g / 10 min to 1.9 g / 10 min.

[0039] Embodiments are conditioned on the polymer having a melt index (I 5is conditional on being able to have. All individual values and sub-ranges from 0.001 g / 10 min to 1000 g / 10 min are included. For example, the polymer may have a melt index (I 5 ) that can be.

[0040] Embodiments are conditional on the polymer being able to have a melt index (I 21 ) measured by D1238 (at a load of 190 °C and 21 kg) in the range of 0.001 g / 10 min to 1000 g / 10 min. All individual values and sub-ranges from 0.001 g / 10 min to 1000 g / 10 min are included. For example, the polymer may have a melt index (I 21 ) that can be.

[0041] Embodiments are conditional on the polymer being able to have an Mn (number average molecular weight) of 5,000 to 98,000. All individual values and sub-ranges from 5,000 to 98,000 are included. For example, the polymer may have an Mn with a lower limit of 5,000, 6,000, 16,000, or 28,000 and an upper limit of 98,000, 75,000, 69,000, 55,000, 45,000, or 35,000. Mn can be determined by gel permeation chromatography (GPC) as is known in the art.

[0042] Embodiments are conditional on the polymer being able to have a molecular weight distribution of 2.90 to 21.00, determined as Mw / Mn (weight average molecular weight / number average molecular weight). All individual values and sub-ranges from 2.90 to 21.00 are included. For example, the polymer may have an Mw / Mn with a lower limit of 2.90, 3.00, 3.50, 4.00, or 4.50 and an upper limit of 21.00, 20.00, 8.00, 7.50, 7.00, or 6.50. In some embodiments, Mw / MN can be in the range of 2.90 to about 4.00. Mw / Mn can be determined by GPC analysis as described below.

[0043] Embodiments provide that the polymer can have a melting temperature of 100 to 165 °C. All individual values and sub-ranges from 100 to 165 °C are included. For example, the polymer can have a melting temperature from a lower limit of 100, 105, or 110 °C to an upper limit of 165, 160, or 155 °C. The melting temperature can be determined by differential scanning calorimetry according to ASTM D3418-08.

[0044] Embodiments are conditional on the polymer having a density of 0.890 g / cm 3 to 0.970 g / cm 3 . All individual values and sub-ranges from 0.890 to 0.970 g / cm 3 are included. For example, the polymer can have a density from a lower limit of 0.890, 0.900, 0.910, or 0920 g / cm 3 to an upper limit of 0.970, 0.960, 0.950, or 0.940 g / cm 3 . The density can be determined according to ASTM D-792-13, Standard Test Method for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, e.g., in liquid 2-propanol). The results are reported in units of grams per cubic centimeter (g / cm 3 ).

[0045] Gel Permeation Chromatography (GPC) Test Method: Weight Average Molecular Weight Test Method: Using the chromatogram obtained with a high-temperature gel permeation chromatography apparatus (HTGPC, Polymer Laboratories), M w , number average molecular weight (M n ), and M w / M nDetermine. The HTGPC is equipped with a transfer line, a differential refractive index detector (DRI), and three Polymer Laboratories PLgel 10μm Mixed-B columns, all of which are housed in an oven maintained at 160°C. The method uses a solvent consisting of TCB treated with BHT at a nominal flow rate of 1.0 milliliter per minute (mL / min.) and a nominal injection volume of 300 microliters (μL). Dissolve 6 grams of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent-grade 1,2,4-trichlorobenzene (TCB), and filter the resulting solution through a 0.1 micrometer (μm) Teflon filter to obtain the solvent. Degas the solvent with an in-line degasser before it enters the HTGPC apparatus. Calibrate the column using a series of monodisperse polystyrene (PS) standards. Separately, prepare a test polymer of known concentration dissolved in the solvent by heating a known amount of the test polymer in a known volume of the solvent with continuous shaking at 160°C for 2 hours to obtain a solution. (Measure all amounts by weight.) The target solution concentration c of the test polymer is 0.5 to 2.0 milligrams of polymer per milliliter of solution (mg / mL), and a lower concentration of c is used for high molecular weight polymers. Purge the DRI detector before running each sample. Next, increase the flow rate in the apparatus to 1.0 mL / min and stabilize the DRI detector for 8 hours before injecting the first sample. Use the relationship between column calibration and universal calibration to calculate M w and M n Calculate. Calculate the MW at each elution volume using the following equation.

Equation

[0334] -

[0341] of US2006 / 0173123. Plot dW / dLog(MW) on the y-axis against Log(MW) on the x-axis to obtain the GPC chromatogram (Log(MW) and dW / dLog(MW) are as defined above).

[0046] The polymer can be used, in particular, in many articles such as films, fibers, nonwovens and / or woven fabrics, extruded articles, and / or molded articles.

[0047] Also provided is a bimodal catalyst system comprising a titanium biphenylphenol polymerization precatalyst of formula I or an activated reaction product thereof, and at least one olefin polymerization catalyst (second catalyst) that is not a titanium biphenylphenol polymerization precatalyst of formula I or an activated reaction product thereof. Such a second catalyst can be a Ziegler-Natta catalyst, a chromium-based catalyst (e.g., the so-called Phillips catalyst), a metallocene catalyst with or without an indenyl ring (e.g., a metallocene catalyst containing unsubstituted and / or alkyl-substituted cyclopentadienyl rings), a Group 15 metal-containing catalyst compound described in paragraphs

[0041] to

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

[0036] to

[0080] of US2018 / 0002464A1.

[0048] The titanium biphenylphenol polymerization precatalyst of formula I, as well as other components discussed herein such as activators and / or additional polymerization components, can be used with a carrier. The "carrier", which can also be referred to as a "support", refers to any carrier material including porous carrier materials such as talc, inorganic oxides, and inorganic chlorides.

[0049] The titanium biphenylphenol polymerization precatalyst of formula I, as well as other components discussed herein, can be supported on the same or separate carriers, or one or more of the components can be used in an unsupported form. Using a carrier can be achieved by any technique used in the art. One or more embodiments provide that a spray drying process is used. Spray drying processes are well known in the art. The carrier can be functionalized.

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

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

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

[0053] The carrier material can 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 / cm 3 ³, and an average particle size in the range of about 5 to about 500 μm. More preferably, the surface area of the carrier material is in the range of about 50 to about 500 m² / g, the pore volume is in the range of about 0.5 to about 3.5 g / cm 3 ³, and the average particle size is in the range of about 10 to about 200 μm. Most preferably, the surface area of the carrier material is in the range of about 100 to about 400 m² / g, the pore volume is in the range of about 0.8 to about 3.0 g / cm 3 ³, and the average particle size is in the range of about 5 to about 100 μm. The average pore diameter of the carrier typically has a pore diameter in the range of 10 to 1000 Å, preferably 50 to about 500 Å, and most preferably 75 to about 350 Å.

[0054] The molar ratio of the metal in the activator to the metal in the biphenylphenol polymerization pre-catalyst of Formula I can be from 1000:1 to 0.5:1, from 300:1 to 1:1, or from 150:1 to 1:1. To facilitate the combination of any two or more components, one or more diluents, such as fluids, can be used. For example, the titanium biphenylphenol polymerization pre-catalyst of Formula I and the activator can be combined together in the presence of toluene or another non-reactive hydrocarbon or hydrocarbon mixture. In addition to toluene, other suitable diluents can include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. Next, either a dried or toluene-mixed carrier can be added to the mixture, or the titanium biphenylphenol polymerization pre-catalyst / activator can be added to the carrier. The slurry can be fed to a reactor for the polymerization process, and / or the slurry can be dried (e.g., spray dried) before being fed to a reactor for the polymerization process.

[0055] The polymerization process can be used using known apparatus and reaction conditions, such as known polymerization conditions. The polymerization process is not limited to any particular type of polymerization system. As an example, the polymerization temperature can range from about 0 °C to about 300 °C at atmospheric pressure, a pressure lower than atmospheric pressure, or a pressure higher than atmospheric pressure. Embodiments provide a method of making a polyolefin polymer, the method comprising contacting an olefin with a titanium biphenylphenol polymerization catalyst under polymerization conditions to polymerize the olefin, thereby making a polyolefin polymer, as described herein.

[0056] One or more embodiments are conditioned on the polymer being made via 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 at temperatures in the range of 30 to 130 °C, 65 °C to 110 °C, 75 °C to 120 °C, or 80 °C to 120 °C. For one or more embodiments, the temperature can be 80 °C, 90 °C, or 100 °C. A stirred and / or fluidized bed gas phase polymerization system can 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 at a rate sufficient to maintain a bed of solid particles in suspension under the reaction conditions and in the presence of a catalyst composition, for example, a composition containing an activated titanium phenylphenol prepolymerization catalyst of formula I. The stream containing unreacted monomer can be continuously withdrawn from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled to the reactor. The product, i.e., the polymer, can be removed from the reactor, and a substituted monomer can be added to the recycle stream. A gas inert to the catalyst composition and reactants can also be present in the gas stream. The polymerization system can include, for example, a single reactor or two or more consecutive reactors.

[0058] The feed stream to the polymerization process can contain an olefin monomer, a non-olefin gas such as nitrogen and / or hydrogen, and further can contain one or more non-reactive alkanes that are condensable in the polymerization process and can be used to remove the heat of reaction. Exemplary non-reactive alkanes include, but are not limited to, propane, butane, isobutane, pentane, isopentane, hexane, their isomers, and their derivatives. The feed can be introduced into the reactor at a single or multiple different locations.

[0059] In the polymerization process, the polymerization catalyst can be continuously fed to the reactor. A gas inert to the polymerization catalyst, such as nitrogen or argon, can be used to carry the polymerization catalyst to the reactor bed.

[0060] In one embodiment, the polymerization catalyst can be provided as a slurry in mineral oil or a liquid hydrocarbon or mixture such as propane, butane, isopentane, hexane, heptane or octane. The slurry can be delivered to the reactor with a carrier fluid such as nitrogen or argon, or with a liquid such as isopentane or other C 3 ~C 8 alkanes.

[0061] For the polymerization process, hydrogen can be used at a gas molar ratio of hydrogen to ethylene in the reactor in the range of about 0.0 - 1.0, 0.01 - 0.7, 0.03 - 0.5, or 0.005 - 0.4. Many embodiments use hydrogen gas. In some embodiments, the gas molar ratio of hydrogen to ethylene in the reactor can be 0.0068, 0.0016, or 0.0011.

[0062] Some aspects of the present disclosure are provided as follows.

[0063] Aspect 1 provides a titanium biphenylphenol prepolymerization catalyst of formula I, [Chemical formula]

[0064] wherein each of R 7 and R 8 is independently C 1 ~C 20 alkyl, aryl, aralkyl, or hydrogen, and each of R 5 and R 10 is independently C 1 ~C 20 alkyl, aryl, aralkyl, halide, or hydrogen, and each of R 2 and R 13 is independently C 1 ~C 20 alkyl, aryl, aralkyl, or hydrogen, and each of R 15 and R 16Each of them is 2,7-disubstituted carbazol-9-yl or 3,6-disubstituted carbazol-9-yl, and L is C that forms a 2-carbon bridge, a 3-carbon bridge, or a 4-carbon bridge between the two oxygen atoms to which L is covalently bonded. 2 ~C 4 alkylene, and each of R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 is independently a halide or hydrogen, and each X is independently a hydrocarbyl, a halide, a pseudohalide, a hydroxy group, an alkoxy group, a phenoxy group, an aryloxy group, or hydrogen, and at least one X is not a hydrocarbyl.

[0065] Embodiment 2 provides the precatalyst of Embodiment 1, wherein each of R 7 and R 8 is C 1 alkyl or each of R 7 and R 8 is hydrogen.

[0066] Embodiment 3 provides the precatalyst of Embodiment 1 or 2, wherein each of R 5 and R 10 is a dialkyl- or trialkyl-substituted silyl.

[0067] Embodiment 4 provides the precatalyst of Embodiment 1, wherein each of R 5 and R 10 is octyldimethylsilyl.

[0068] Embodiment 5 provides the precatalyst of Embodiment 1 or 2, wherein each of R 5 and R 10 is fluorine.

[0069] Embodiment 6 provides the precatalyst that is any one of Embodiments 1 to 5, wherein each of R 2 and R 13Each of them is 1,1 - dimethylethyl.

[0070] Aspect 7 provides a pre - catalyst of any one of Aspects 1 - 6, wherein R 15 and R 16 each of which is 2,7 - di - t - butylcarbazol - 9 - yl or 3,6 - di - t - butylcarbazol - 9 - yl.

[0071] Aspect 8 provides a pre - catalyst of any one of Aspects 1 - 7, wherein L is a saturated C 3 alkylene.

[0072] Aspect 9 provides a pre - catalyst of any one of Aspects 1 - 8, wherein each X is chlorine.

[0073] Aspect 10 provides a pre - catalyst of any one of Aspects 1 - 9, further comprising a silica carrier without an activator, and the silica carrier without an activator supports the pre - catalyst.

[0074] Aspect 11 provides a method for preparing a titanium biphenylphenol polymerization catalyst, which method comprises contacting a titanium biphenylphenol polymerization pre - catalyst of Formula I of any one of Aspects 1 - 10 with an activator under activation conditions to activate the titanium biphenylphenol polymerization pre - catalyst of Formula I, thereby preparing a titanium biphenylphenol polymerization catalyst.

[0075] Aspect 12 further provides the method of Aspect 11, which comprises contacting a solution of a titanium biphenylphenol polymerization pre - catalyst of Formula I dissolved in an alkane solvent and without an activator with a silica carrier containing a spray - dried activator thereon to prepare a titanium biphenylphenol polymerization catalyst on the silica carrier.

[0076] Aspect 13 provides a titanium biphenylphenol polymerization catalyst prepared by the method of Aspect 11 or 12.

[0077] Aspect 14 provides a method for producing polyethylene, which includes polymerizing an olefin monomer in a single gas-phase polymerization reactor in the presence of the titanium biphenylphenol polymerization catalyst of Aspect 13 to produce a polyethylene composition.

[0078] Aspect 15 provides the method of Aspect 14, further including preparing a titanium biphenylphenol polymerization catalyst before the polymerization step and feeding the titanium biphenylphenol polymerization catalyst to a single gas-phase polymerization reactor.

Examples

[0079] The titanium biphenylphenol polymerization pre-catalyst of formula (i) was prepared as follows. Inside a glove box, a 40 milliliter (mL) glass vial dried in an oven was loaded with a ligand of formula A (0.500 grams, 0.407 mmol), diethyl ether [Et2O] (20 mL, available from Fisher Scientific), and a magnetic stir bar. The ligand of formula A (2’,2”-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5’-fluoro 5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol) was prepared as described in WO2012 / 027,448, the entire content of WO2012 / 027,448 is incorporated herein by reference. The contents of the vial were stirred until the ligand of formula A dissolved, and then the contents of the vial were cooled to about -30 degrees Celsius (°C). Next, titanium(IV) chloride [TiCl4] (45 μL, 0.407 mmol, available from Aldrich) was slowly added to the stirred solution of the ligand to form a mixture. Immediately, a color change to dark red was observed, and then the mixture was stirred at room temperature overnight. The solvent was removed in vacuo, and the resulting residue was suspended in cold pentane and then filtered to obtain a red solid, which was washed with pentane (0.55 g, 100% yield). The presence of the titanium biphenylphenol polymerization pre-catalyst of formula i was 1 confirmed by 1H NMR analysis. 1 1H NMR (400 MHz, C 6 D 6)δ8.60(d,J=1.9Hz,2H),8.40(d,J=1.9Hz,2H),7.77-7.57(m,6H),7.49(d,J=2.4Hz,2H),7.40(d,J=8.6Hz,2H),7.22(d,J=2.4Hz,2H),6.91(dd,J=8.5,3.2Hz,2H),6.18-6.03(m,2H),5.78(dd,J=9.4,4.5Hz,2H),3.86(d,J=8.2Hz,2H),3.56-3.39(m,2H),1.54(s,18H),1.49-1.43(m,6H),1.37(s,18H),1.11(s,6H),1.08(s,6H),0.76(s,18H). 13 C NMR(101MHz,C 6 D 6 )δ214.97,192.01,160.72,157.64,152.98,146.21,143.93,143.54,140.88,140.81,131.64,127.12,126.19,126.04,125.79,123.84,123.59,119.12,118.89,117.80,116.76,116.56,111.58,109.82,57.49,38.81,35.36,35.17,34.79,32.83,32.68,32.57,32.44,32.33,32.10,31.29,29.54,23.07,14.62.). 19 F NMR(376MHz,C 6 D 6 )δ-122.45.

[0080]

Chem.

[0081] The titanium biphenylphenol polymerization pre-catalyst of formula (ii) was prepared using the same components and methodology as the titanium biphenylphenol polymerization pre-catalyst of formula (i), except that the ligand of formula B (0.500 g, 0.398 mmol) was used instead of the ligand of formula A (0.087 g, 16% yield). The ligand of formula B (2’,2”‘-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5’-fluoro-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)-[l,l’-biphenyl]-2-ol) was prepared as described in WO2014 / 105411, the entire content of WO2014 / 105411 is incorporated herein by reference. The presence of the titanium biphenylphenol polymerization pre-catalyst of formula (ii) was 1 confirmed by 1H NMR analysis. 1 1H NMR (400 MHz, C 6 D 6 ) δ 8.12 (dd, J = 37.8, 8.2 Hz, 4H), 7.93 - 7.73 (m, 6H), 7.46 (ddd, J = 21.2, 8.2, 1.6 Hz, 4H), 7.31 (d, J = 2.5 Hz, 2H), 6.78 (dd, J = 8.9, 3.2 Hz, 2H), 6.05 (dd, J = 8.3, 3.1 Hz, 2H), 3.86 (dt, J = 10.4, 5.1 Hz, 2H), 3.16 (dt, J = 11.0, 5.6 Hz, 2H), 1.67 (d, J = 14.5 Hz, 2H), 1.58 (s, 18H), 1.52 (d, J = 14.5 Hz, 2H), 1.36 (s, 18H), 1.31 (2, 6H), 1.18 (s, 6H), 1.13 (s, 6H), 0.84 (s, 18H). 13 13C NMR (101 MHz, C 6 D 6)δ161.92, 159.49, 157.44, 153.97, 153.94, 150.79, 149.78, 149.05, 148.03, 144.45, 142.91, 142.58, 142.52, 134.78, 134.69, 133.98, 133.89, 132.75, 128.88, 127.43, 126.72, 124.61, 121.47, 120.72, 120.11, 119.86, 118.71, 118.45, 118.39, 118.23, 117.41, 117.18, 110.27, 108.65, 76.43, 57.94, 38.84, 35.87, 35.81, 33.42, 33.03, 32.74, 32.36, 32.32, 32.16, 29.96, 29.63, 17.71.

[0082] [Chemical formula]

[0083] The titanium biphenylphenol polymerization pre-catalyst of formula (iii) was prepared using the same components and method as the titanium biphenylphenol polymerization pre-catalyst of formula i, but instead of the ligand of formula A (1.098 g, yield 26%), the ligand of formula C (4.000 g, 2.563 mmol) and pentane (available from Sigma Aldrich) as the solvent were used. The ligand of formula C was prepared as described in WO2017 / 058,981, the entire content of which is incorporated herein by reference. The presence of the titanium biphenylphenol polymerization pre-catalyst of formula (iii) was 1 confirmed by 1H NMR analysis. 1 1H NMR (400 MHz, C 6 D 6) δ 8.15 (d, J = 8.2 Hz, 2H), 8.04 - 7.94 (m, 4H), 7.84 (dd, J = 14.6, 2.1 Hz, 4H), 7.67 (d, J = 2.5 Hz, 2H), 7.53 - 7.45 (m, 4H), 7.36 (dd, J = 8.3, 1.6 Hz, 2H), 7.08 (d, J = 1.6 Hz, 2H), 4.13 (dt, J = 10.6, 5.2 Hz, 2H), 3.43 (dt, J = 10.9, 5.6 Hz, 2H), 1.77 (d, J = 14.5 Hz, 2H), 1.65 (s, 6H), 1.64 (d, J = 13.5 Hz, 2H), 1.63 - 1.58 (m, 2H), 1.61 (s, 18H), 1.37 (s, 6H), 1.32 (s, 18H), 1.44 - 1.17 (m, 24H), 0.94 - 0.84 (m, 4H), 0.91 (s, 18H), 0.60 (t, J = 7.7 Hz, 4H), 0.09 (s, 6H), 0.08 (s, 6H). 13 C NMR (101 MHz, C 6 D 6 ) δ 158.73, 157.86, 150.50, 147.87, 144.02, 142.62, 142.54, 139.05, 137.49, 137.41, 134.32, 131.92, 131.53, 129.05, 127.37, 126.34, 124.61, 121.42, 120.74, 119.91, 119.87, 118.26, 110.29, 108.71, 76.14, 58.12, 38.93, 35.82, 34.40, 33.37, 32.75, 32.71, 32.39, 32.10, 30.31, 30.14, 30.12, 29.78, 24.71, 23.45, 17.88, 16.27, 14.74, -2.66, -2.75.

[0084]

Chem.

[0085] As used herein, "Me" refers to methyl and "t-Bu" refers to tert-butyl.

[0086] The prepolymerization precatalysts of formulas (iv) and (v) were prepared as described in WO2017 / 058981A1, the entire content of WO2017 / 058981A1 being incorporated herein by reference.

Chem.

[0087]

Chem.

[0088] The activation of the titanium biphenylphenol polymerization precatalysts of formulas i, ii, iii, iv, and v was carried out by either Method I or Method II, as detailed below.

[0089] Method I:

[0090] Example 1 (EX1), an activated titanium biphenylphenol polymerization catalyst of formula I, was prepared according to Method I as follows. Inside a nitrogen-purged glove box, a glass bottle dried in an oven was charged with 2.65 grams (g) of treated fumed silica (CABOSIL TS-610, available from W.R. Grace) slurried with 75 g of toluene (available from Aldrich), and a stir bar, and stirred until well dispersed. A 10 wt% solution of 22 g of methylaluminoxane (MAO) (available from W.R. Grace as 10 wt% in toluene) was added to the bottle to form a mixture. The mixture was magnetically stirred for 15 minutes, then the biphenylphenol polymerization catalyst of Structure III (0.303 g) was added, and the mixture was stirred for 30 - 60 minutes. The mixture was spray dried using a Buchi Mini Spray Dryer B-290 with the following parameters to obtain the dried, activated titanium biphenylphenol polymerization catalyst of Example 1. Set temperature -185 °C, outlet temperature -100 °C (min), aspirator -95, and pump speed -150 rpm.

[0091] Example 2 (EX2) was prepared in the same manner as Example 1, with the modification that the catalyst of Example 2 was used, as shown in Table 1.

[0092] Example 3 (EX3) was prepared in the same manner as Example 1, with the modification that the catalyst of Example 3 was used, as shown in Table 1.

[0093] Method II:

[0094] The activated titanium biphenylphenol polymerization catalysts of Examples 4 - 11 (EX4 - 11), and Comparative Examples 1 - 7 (CE1 - 7), which are of Formula I, were prepared according to Method II as follows.

[0095] For Example 4, a 0.9 mg / mL suspension of the titanium biphenylphenol polymerization pre - catalyst of Formula iii in hexane (a: 1.3 mg, 0.21 mL, 0.75 μmol Ti, b: 2.5 mg, 0.42 mL, 1.5 μmol, available from Aldrich) was injected as a solution without the activator into a bomb containing the activator in the form of spray - dried methylaluminoxane in the amounts shown in Table 1 (e.g., 0.0015 g) to produce the activated and supported titanium biphenylphenol polymerization catalyst of Example 4.

[0096] The activated titanium biphenylphenol polymerization catalysts of Examples 5 - 11 were prepared as in Example 4, with the modification that the respective catalysts and amounts of catalysts of Examples 5 - 11 were used, as shown in Table 1.

[0097] The activated catalysts of Comparative Examples 1 - 7 were prepared as in Example 4, with the modification that the respective catalysts and amounts of catalysts of Comparative Examples 1 - 7 were used, as shown in Table 1.

[0098] Titanium titanium

[0099] The ethylene / 1-hexene copolymerizations of EX1 to 11 and CE1 to 7 were carried out in the gas phase in a 2 L semi-batch autoclave polymerization reactor equipped with a mechanical stirrer as follows. The reactor was first dried for 1 hour, charged with 200 g of sodium chloride (NaCl), and dried by heating at 100 °C for 30 minutes under nitrogen. After drying, 5 g of silica-supported methylaluminoxane (SMAO) was introduced as a scavenger under nitrogen pressure. After adding SMAO, the reactor was sealed and the components were stirred. Next, hydrogen (H 2 preload) and hexene (C6 / C2 ratio as shown below for each condition) were charged, and then the reactor was pressurized with ethylene (230 psi). Once the system reached a steady state, the type and amount of each activated catalyst (activated by Method I or II) specified in Table 1 for each of Examples 1 to 11 and Comparative Examples 1 to 7 were charged into the reactor at 80 °C to initiate polymerization. The temperature of the reactor was set to 90 or 100 °C and maintained at this temperature during a 1-hour operation. The operation was carried out under Conditions 1, 2, 3, or 4 as shown in Table 1 and detailed below. At the end of the operation, the reactor was cooled, vented, and opened. The resulting product mixture was washed with water and methanol and then dried. The results of Examples 1 to 11 and Comparative Examples 1 to 7 are shown in Table 2.

[0100] Productivity (grams of polymer / gram of catalyst / hour) was determined as the ratio of the polymer produced to the amount of catalyst and activator added to the reactor.

[0101] Mn (number average molecular weight), Mw (weight average molecular weight), z-average molecular weight (Mz), and Mw / Mn (weight average molecular weight / number average molecular weight) were determined by gel permeation chromatography (GPC) as is known in the art.

[0102] The comonomer content incorporated into the polymer (i.e., 1-hexene) (wt%) was determined by high-speed FT-IR spectroscopy for the dissolved polymer in GPC measurements.

[0103] The melt index (MI, I 2 ) can be measured in accordance with ASTM D1238 (190 °C, 2.16 kg weight). The melt index (MI, I 5 ) can be measured in accordance with ASTM D1238 (190 °C, 5 kg). The melt index (MI, I 21 ) can be measured in accordance with ASTM D1238 (190 °C, 21.6 kg).

[0104] Condition 1: C 6 / C 2 Ratio = 0.004, H 2 Preload = 5.02 liters (L), H 2 / C 2 Ratio = 0.0068, C 2 Pressure = 230 pounds per square inch (psi), Condition 2: C 6 / C 2 Ratio = 0.004, H 2 Preload = 1.18 L, H 2 / C 2 Ratio = 0.0016, C 2 Pressure = 230 psi, Condition 3: C 6 / C 2 Ratio = 0.016, H 2 Preload = 0.81 L, H 2 / C 2 Ratio = 0.0011, C 2 Pressure = 230 psi, Condition 4: C6 / C2 ratio = 0.016, H 2 Preload = 0.40 L, H 2 / C 2 = 0.0011, C 2 Pressure = 115 psi.

[0105]

Table 1

[0106]

Table 2

[0107] "NT" did not conduct the test.

[0108] As detailed in Tables 1 and 2, EX1 - 11 provide a titanium biphenylphenol polymerization catalyst and the resulting polymers having suitable properties.

[0109] The titanium biphenylphenol polymerization catalyst of the present disclosure can produce polymers with lower molecular weights than the polymers from the comparative catalysts. For example, under Condition 1 and Catalyst Addition Method II, CE1 and CE2 have Mw values of 259,109 and 202,837 respectively, compared to the Mw values of 105,215 and 102,243 of EX4 and EX5 respectively. That is, the Mw of the polymers obtained from the titanium biphenylphenol polymerization catalyst of the present disclosure can be at least 40 percent lower than the Mw of the comparative polymers. Nevertheless, the titanium biphenylphenol polymerization catalyst still provides other desired properties (Mn, Mz, Mw / Mn ratio, % of comonomer incorporation, I 2 I 5 I 21 , yield, and / or productivity).

[0110] For example, the titanium biphenylphenol polymerization catalyst of the present disclosure can have lower productivity than the comparative catalysts. As detailed in Table 1, EX4 - 11 all have lower productivity than CE1 - 7. Without wishing to be bound by theory, the lower productivity is considered desirable as it may reduce catalyst degradation and / or otherwise improve operability compared to catalysts with high productivity that can cause operability problems in gas phase polymerization reactors.

[0111] In addition, EX4 - 11 demonstrate that the operability of the titanium biphenylphenol polymerization catalyst of the present disclosure can be improved by adopting catalyst addition method II instead of catalyst addition method I. Under conditions 1 and 2, EX4 - 11 (method II) provide higher yields and / or productivity than when the same or similar titanium catalysts were employed in method I (EX1 - 3). Without wishing to be bound by theory, adopting method II reduces catalyst degradation compared to other approaches such as method I for making activated catalysts (e.g., conventionally supported / slurry), which, because the activator and pre - catalyst in the mixture are contacted before spray - drying the mixture, once formed, takes a considerably longer time for the catalyst to decompose. Put another way, EX4 - 11 adopting method II make the activated catalyst using a solution that does not contain (contains no activator at all) an activator until the solution later contacts an activator such as a spray - dried activator, which can then be fed directly / immediately to a gas - phase polymerization reactor (e.g., as a trim catalyst), reducing any catalyst degradation and thereby improving operability. For example, the catalyst can be fed directly to a gas - phase polymerization reactor via in - line trim addition or other mechanisms immediately after the formation of the activated titanium biphenylphenol polymerization catalyst by method II as described herein.

[0112] The titanium biphenylphenol polymerization catalyst of the present disclosure desirably incorporates less comonomer (1 - hexene). For example, under condition 3, CE4 and CE5 have comonomer incorporations of 5.35 and 6.14, respectively, compared to comonomer incorporations of 2.98 and 3.07 percent for EX8 and EX9, respectively. That is, the comonomer incorporation of the polymer obtained from the titanium biphenylphenol polymerization catalyst of the present disclosure can be at least 65 percent less than the comonomer incorporation of the comparative catalysts employed under the same conditions (conditions 2, 3, and 4) and catalyst method. The present specification includes the following aspects. Item 1. A titanium biphenylphenol polymerization pre - catalyst of formula I, [Chemical formula] In the formula, R 7 and R 8 each independently represents C 1 ~C 20 alkyl, aryl, aralkyl or hydrogen, R 5 and R 10 each independently represents C 1 ~C 20 alkyl, aryl, aralkyl, halide, or hydrogen, R 2 and R 13 each independently represents C 1 ~C 20 alkyl, aryl, aralkyl, or hydrogen, R 15 and R 16 each independently represents 2,7-disubstituted carbazole or 3,6-disubstituted carbazole, L forms a C 2 ~C 4 alkylene that forms a 2-carbon bridge, 3-carbon bridge, or 4-carbon bridge between two oxygen atoms to which L is covalently bonded, R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 each independently represents a halide or hydrogen, Each X independently represents hydrocarbyl, halide, pseudohalide, hydroxy group, alkoxy group, phenoxy group, aryloxy group, or hydrogen, and at least one X is not hydrocarbyl. A titanium biphenylphenol polymerization precatalyst of formula I. Item 2. R 7 and R 8 each represents C 1 alkyl, or R 7 and R 8The pre-catalyst according to item 1, wherein each of R 5 10 5 < is hydrogen. Item 3. The pre-catalyst according to item 1 or 2, wherein R 5 10 is a dialkyl or trialkyl substituted silyl. Item 4. The pre-catalyst according to item 3, wherein each of R 5 10 is octyldimethylsilyl. Item 5. The pre-catalyst according to item 1 or 2, wherein R 5 and R 10 are each fluorine. Item 6. The pre-catalyst according to any one of items 1 to 5, wherein R 2 and R 13 are each 1,1-dimethylethyl. Item 7. The pre-catalyst according to any one of items 1 to 6, wherein each of R 15 and R 16 is 2,7-di-t-butylcarbazole or 3,6-di-t-butylcarbazole. Item 8. The pre-catalyst according to any one of items 1 to 7, wherein L is a saturated C 3 alkylene. Item 9. The pre-catalyst according to any one of items 1 to 8, wherein each X is chlorine. Item 10. The pre-catalyst according to any one of items 1 to 9, further comprising an activator-free silica support, the activator-free silica support supporting the catalyst. Item 11. A method of making a titanium biphenyl phenol polymerization catalyst, comprising contacting a titanium biphenyl phenol polymerization pre-catalyst of formula I according to any one of items 1 to 10 with an activator under activating conditions to activate the titanium biphenyl phenol polymerization pre-catalyst of formula I, thereby making the titanium biphenyl phenol polymerization catalyst. Item 12. ​​​​​​A method according to claim 11, further comprising contacting a solution containing no activator of the titanium biphenylphenol polymerization pre-catalyst of formula I dissolved in an alkane solvent with a silica support containing a spray-dried activator thereon to produce the titanium biphenylphenol polymerization catalyst on the silica support. Claim 13. A titanium biphenylphenol polymerization catalyst produced by the method according to claim 11 or 12. Claim 14. A method for producing polyethylene, comprising: polymerizing an olefin monomer in a single gas-phase polymerization reactor in the presence of the titanium biphenylphenol polymerization catalyst according to claim 13 to produce a polyethylene composition. Claim 15. Before the polymerization step, producing the titanium biphenylphenol polymerization catalyst; and feeding the titanium biphenylphenol polymerization catalyst to the single gas-phase polymerization reactor. A method according to claim 14, further comprising the above steps.

Claims

1. 1. A titanium biphenyl phenol polymerization precatalyst of formula I, 【Chemistry 1】 In the formula, R ７ and R ８ Each of the groups independently represents C １ ~C ２０ alkyl, aryl, aralkyl or hydrogen; R ５ and R １０ each is independently dialkyl- or trialkyl-substituted silyl; R ２ and R １３ Each of the groups independently represents C １ ~C ２０ alkyl, aryl, aralkyl, or hydrogen; R １５ and R １６ each of which is a 2,7-disubstituted carbazole or a 3,6-disubstituted carbazole; L forms a 2-carbon bridge, a 3-carbon bridge, or a 4-carbon bridge between the two oxygen atoms to which L is covalently bonded, respectively. ２ ~C ４ is alkylene, R １ , R ３ , R ４ , R ６ , R ９ , R １１ , R １２ , and R １４ each is independently a halide or hydrogen; A titanium biphenylphenol polymerization precatalyst of formula I, wherein each X is independently a hydrocarbyl, a halide, a pseudohalide, a hydroxy group, an alkoxy group, a phenoxy group, an aryloxy group, or hydrogen, and at least one X is not a hydrocarbyl.

2. R ７ and R ８ Each of the above is C １ alkyl or R ７ and R ８ The pre-catalyst of claim 1 , wherein each of is hydrogen.

3. R ５ and R １０ 3. The pre-catalyst of claim 1 or 2, wherein each of is octyldimethylsilyl.

4. R ２ and R １３ The pre-catalyst of any one of claims 1 to 3, wherein each of is 1,1-dimethylethyl.

5. R １５ and R １６ The pre-catalyst of any one of claims 1 to 4, wherein each of is 2,7-di-t-butylcarbazole or 3,6-di-t-butylcarbazole.

6. L is saturated C ３ The pre-catalyst according to any one of claims 1 to 5, which is an alkylene.

7. A pre-catalyst according to any one of claims 1 to 6, wherein each X is chlorine.

8. 8. The pre-catalyst of any one of claims 1 to 7, further comprising an activator-free silica support, said activator-free silica support supporting said pre-catalyst.

9. 10. A method of making a titanium biphenylphenol polymerization catalyst comprising contacting a titanium biphenylphenol polymerization pre-catalyst of formula I according to any one of claims 1 to 8 with an activator under activating conditions to activate said titanium biphenylphenol polymerization pre-catalyst of formula I, thereby making said titanium biphenylphenol polymerization catalyst.

10. 10. The method of claim 9, further comprising contacting an activator-free solution of said titanium biphenylphenol polymerization pre-catalyst of formula I dissolved in an alkane solvent with a silica support containing spray-dried activator on the support to produce a titanium biphenylphenol polymerization catalyst on a silica support.

11. 1. A method of making a polyethylene composition, comprising the steps of:

11. A process comprising polymerizing olefin monomers including ethylene monomer in a single gas phase polymerization reactor in the presence of a titanium biphenylphenol polymerization catalyst made by the process of claim 9 or 10 to make a polyethylene composition.

12. Prior to polymerizing olefin monomers including ethylene monomer, preparing the titanium biphenyl phenol polymerization catalyst; 12. The method of claim 11, further comprising: feeding said titanium biphenyl phenol polymerization catalyst to said single gas phase polymerization reactor.

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