Titanium biphenylphenol polymerization catalyst

Abstract

An embodiment of the present disclosure relates to a titanium biphenylphenol polymerization precursor of formula (I).

Description

Technology Field

[0001] The embodiments of the present disclosure relate to a titanium biphenylphenol polymerization catalyst, more specifically, a titanium biphenylphenol polymerization catalyst of Formula I. Background Technology

[0002] The polymer can be used in a number of products, particularly including films, fibers, nonwovens and / or fabrics, extruded articles, and / or molded articles. The polymer can be prepared by reacting one or more types of monomers in a polymerization reaction in the presence of a polymerization catalyst.

[0003] The present disclosure provides various embodiments comprising a titanium biphenylphenol polymerization precatalyst of Formula I:

[0004]

[0005] In the above equation, R 7 and R 8 Each independently C1 to C 20 alkyl, aryl, aralkyl, or hydrogen; R 5 and R 10 Each independently C1 to C 20 It is an alkyl, aryl, aralkyl, halide, or hydrogen; R 2 and R 13 Each independently C1 to C 20 alkyl, aryl, aralkyl, or hydrogen; R 15 and R 16 is each 2,7-disubstituted carbozol-9-yl or 3,6-disubstituted-carbozol-9-yl; L is a C2-C4 alkylene in which L forms a 2-carbon bridge, a 3-carbon bridge, or a 4-carbon bridge, respectively, between two covalently bonded oxygen atoms; and R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14Each is independently a halide or hydrogen; each X is independently a hydrocarbyl, halide, pseudo-halide, hydroxyl group, alkoxy group, phenoxy group, aryloxy group, or hydrogen, and at least one X is not hydrocarbyl. As used herein, the precatalyst is a catalytic compound prior to exposure to an activator.

[0006] A method for preparing a titanium biphenylphenol polymerization catalyst, wherein the method comprises the step of preparing a titanium biphenylphenol polymerization catalyst by contacting a titanium biphenylphenol polymerization precursor catalyst of Formula I with an activator under activation conditions to activate the titanium biphenylphenol polymerization precursor catalyst of Formula I;

[0007] Titanium biphenylphenol polymerization catalyst; and

[0008] A method for manufacturing polyethylene comprises the step of polymerizing olefin monomers in a single-phase polymerization reactor in the presence of a titanium biphenylphenol polymer catalyst to produce the polyethylene composition described herein. Specific details for implementing the invention

[0009] The titanium biphenylphenol polymerization precatalyst of the present invention can be represented by the chemical formula I:

[0010]

[0011] In the above equation, R 7 and R 8 Each independently C1 to C 20 It is alkyl, aryl, aralkyl, or hydrogen;

[0012] R 5 and R 10 Each independently C1 to C 20 It is an alkyl, aryl, aralkyl, halide, or hydrogen;

[0013] R 2 and R 13 Each independently C1 to C 20 It is alkyl, aryl, aralkyl, or hydrogen;

[0014] R 15 and R 16 are 2,7-disubstituted carbosol or 3,6-disubstituted carbosol, respectively;

[0015] L is a C2-C4 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;

[0016] R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 Each is independently a halide or hydrogen;

[0017] Each X is independently a hydrocarbyl, halide, pseudo-halide, hydroxyl group, alkoxy group, phenoxy group, aryloxy group, or hydrogen, and at least one X is not hydrocarbyl.

[0018] Surprisingly, a polymerization catalyst prepared using the titanium biphenylphenol polymerization precursor of the present disclosure can produce polymers with lower molecular weight compared to polymers prepared with other (non-inventive) polymerization catalysts under similar polymerization conditions described in detail herein. Polymers with lower molecular weight are desirable in some applications.

[0019] Furthermore, surprisingly, the titanium biphenylphenol polymerization catalyst of the present disclosure may have lower catalyst productivity than other polymerization catalysts under similar polymerization conditions described in detail herein. Lower catalyst productivity is desirable in some processes.

[0020] Furthermore, surprisingly, the titanium biphenylphenol polymerization catalyst of the present disclosure can produce polymers containing fewer comonomers compared to polymers produced with other polymerization catalysts under similar polymerization conditions described in detail herein. Incorporating fewer comonomers is desirable in some applications.

[0021] Additionally, surprisingly, the titanium biphenylphenol polymerization catalyst of the present disclosure can provide improved reactor operability as described in detail herein.

[0022] As mentioned, R represented in Chemical Formula I 7 and R 8 Each independently C1 to C 20 It may be an alkyl, aryl, aralkyl, or hydrogen. One or more embodiments are R 7 and R 8 Each of these provides hydrogen. One or more embodiments are R 7 and R 8 Each of these provides a C1 alkyl, for example, methyl.

[0023] As used herein, "alkyl" includes linear, branched, and cyclic paraffin radicals lacking one hydrogen. Thus, for example, CH3 groups ("methyl") and CH3CH2 groups ("ethyl") are examples of alkyls.

[0024] As used herein, "aryl" includes phenyl, naphthyl, pyridyl, and other radicals, and its molecules have ring structural characteristics such as benzene, naphthylene, phenanthrene, and anthracene. "Aryl" is C6 to C 20 It is understood that it can be an aryl. For example, the C6H5- aromatic structure is "phenyl," and the -C6H4- aromatic structure is "phenylene."

[0025] As used herein, "araclel," which may also be called "arylalkyl," is an alkyl having an aryl pendant therefrom. "Araclel" is C7 to C 20 It is understood that it can be an aryl. "Alkylaryl" is an aryl having one or more alkyl group pendants therefrom.

[0026] As mentioned, R represented in Chemical Formula I 5 and R 10 Each independently C1 to C 20It is an alkyl, aryl, aralkyl, halide, or hydrogen. As used herein, "hydrocarbyl" includes aliphatic, cyclic, olefinic, acetyleneic, and aromatic radicals (i.e., hydrocarbon radicals) comprising a carbon lacking one hydrogen and hydrogen. One or more embodiments each R 5 and R 10 Each of these is provided to be a dialkyl or trialkyl substituted silyl. One or more embodiments are R 5 and R 10 Each of these provides octyl dimethyl silyl. One or more embodiments are R 5 and R 10 Each of these provides a halide. One or more embodiments are R 5 and R 10 Each of these provides fluorine.

[0027] As mentioned, R represented in Chemical Formula I 2 and R 13 is independently C1 to C 20 It is an alkyl, aryl, aralkyl, or hydrogen. One or more embodiments are R 2 and R 13 Each of these provides 1,1-dimethyl ethyl.

[0028] As mentioned, R represented in Chemical Formula I 15 and R 16 Each may independently be 2,7-disubstituted carbozol-9-yl or 3,6-disubstituted carbozol-9-yl. As used herein, "disubstituted carbozol-9-yl" refers to a polycyclic aromatic hydrocarbon comprising two 6-membered benzene rings fused to each side of a 5-membered nitrogen-containing ring, each of which is substituted, and nitrogen (at the 9-position of the carbozol ring) is the linking point. For example, one or more embodiments are R 15 and R 16 This provides 2,7-di-t-butylcarbazole-9-yl or 3,6-di-t-butylcarbazole-9-yl, respectively.

[0029] As mentioned, L in Formula I is a C2-C4 alkylene that forms a 2-carbon bridge, a 3-carbon bridge, or a 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded. One or more embodiments provide that L is a saturated C3 alkyl.

[0030] As mentioned, R represented in Chemical Formula I 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 Each is independently a halide or hydrogen. One or more embodiments are R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 Each provides that it is hydrogen.

[0031] As mentioned, each X represented in Formula I is independently a hydrocarbyl, halide, pseudo-halide, hydroxyl group, alkoxy group, phenoxy group, aryloxy group, or hydrogen, and at least one X is not independently a hydrocarbyl. One or more embodiments provide that each X is chlorine. As used herein, pseudo-halide refers to a chemical compound that is not a halide but is a halide analog in terms of charge and reactivity. Examples of pseudo-halides include azido, cyano, isocyano, sulfanido, thiocyano, trilate, tosyl, and tosylate.

[0032] As shown in Chemical Formula I, the central atom is titanium (Ti).

[0033] The R group (R of Chemical Formula I described herein) 1 to R 16) and X are each independently substituted or not substituted. As used herein, "substituted" indicates that the group described following this term has at least one moiety in place of one or more hydrogens at any position, said moiety being 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 C1 to C1 20 Alkyl group, C2 to C 10 It is selected from groups such as alkenyl groups and combinations thereof. "Disubstituted" refers to the presence of two or more substituents at any position, and the moiety is a halogen radical, hydroxyl group, carbonyl group, carboxyl group, amine group, phosphine group, alkoxy group, phenyl group, naphthyl group, C1 to C 20 Alkyl group, C2 to C 10 It is selected from groups such as alkenyl groups and combinations thereof.

[0034] 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 by a number of processes used to prepare known catalysts, for example, with conventional solvents, reaction conditions, reaction times, and separation procedures.

[0035] One or more embodiments provide a polymerization catalyst. The polymerization catalyst may be prepared by the step of providing an activated titanium biphenylphenol polymerization catalyst by contacting a titanium biphenylphenol polymerization precursor of formulas i, ii, iii, iv, and / or v described herein with an activator under activation conditions such as those described herein. Activation conditions are well known in the art.

[0036] As used herein, “activator” refers to any supported or unsupported compound or combination of compounds capable of activating a complex or a catalytic component, for example, by generating a cationic species of the catalytic component. For example, this may include the removal of at least one leaving group, for example, the “X” group described herein, from the metal center of the complex / catalytic component, for example, a metal complex of Formula I. The activator may also be referred to as a “co-catalyst.” As used herein, “leaving group” refers to one or more chemical moieties bonded to a metal atom, which can be removed by the activator to generate an active species for olefin polymerization.

[0037] The activator may include Lewis acids or non-coordinating ionic activators or ionizing activators, or any other compounds including Lewis bases, aluminum alkyls and / or traditional types of co-catalysts. In addition to the methylaluminoxane (“MAO”) and modified methylaluminoxane (“MMAO”) mentioned above, exemplary activators include aluminoxane or modified aluminoxane and / or neutral or ionic ionizing compounds, e.g., dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis(3,5-(CF3)2phenyl)borate, triphenylcarbenium tetrakis(3,5-(CF3)2phenyl)borate, dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, dimethylanilinium tetrakis(pentafluorophenyl)aluminate, triphenylcarbenium tetrakis(pentafluorophenyl)aluminate, dimethylanilinium It may include, but is not limited to, tetrakis(perfluoronaphthyl)aluminate, triphenylcarbenium tetrakis(perfluoronaphthyl)aluminate, tris(perfluorophenyl)boron, tris(perfluoronaphthyl)boron, tris(perfluorophenyl)aluminate, tris(perfluoronaphthyl)aluminate, or any combination thereof.

[0038] Aluminoxane can be described as an oligomeric aluminum compound having an -Al(R)-O- subunit, 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 prepared by the hydrolysis of each trialkylaluminum compound. MMAO can be prepared by the hydrolysis of trimethylaluminum and higher trialkylaluminums, e.g., triisobutylaluminum. Various known methods exist for preparing aluminoxane and modified aluminoxane. Aluminoxane may comprise modified methylaluminoxane (“MMAO”) type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane type 3A discussed in U.S. Patent No. 5,041,584). Sources of MAO may be, for example, solutions having about 1 wt% to about 50 wt% of MAO. Commercially available MAO solutions may include 10 wt% and 30 wt% MAO solutions available from Albemarle Corporation, Batten Rouge, Louisiana.

[0039] One or more organo-aluminum compounds, such as one or more alkylaluminum compounds, may be used with aluminoxan. 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.

[0040] A titanium biphenylphenol polymerization catalyst prepared from a titanium biphenylphenol polymerization precursor of Formula I can be used to produce a polymer. For example, the titanium biphenylphenol polymerization catalyst can be brought into contact with an olefin under polymerization conditions to produce a polymer, for example, a polyolefin polymer.

[0041] As used herein, "polymer" refers to a polymer having two or more identical or different polymer units derived from one or more different monomers, such as a homopolymer, copolymer, terpolymer, etc. "Homogenizer" is a polymer having identical polymer units. "Copolymer" is a polymer having two or more different polymer units. "Terpolymer" is a polymer having three different polymer units. With respect to polymer units, "different" indicates that the polymer units are different or isomerically different by at least one atom. Accordingly, the definition of copolymer as used herein includes terpolymers, etc. As used herein, "polymerization process" is a process used to manufacture a polymer.

[0042] The embodiments provide that the polymer may be a polyolefin polymer. As used herein, “olefin,” which may be referred to as “alkene,” refers to a linear, branched, or cyclic compound comprising carbon and hydrogen and having at least one double bond. As used herein, when a polymer or copolymer is referred to as comprising, for example, an olefin, the olefin present in such polymer or copolymer is a polymerized form of the olefin. For example, when a copolymer is considered to have an ethylene content of 75% to 85% by weight, the polymer units in the copolymer are understood to be derived from ethylene in the polymerization reaction, and the derived units are understood to be present in an amount of 75% to 85% by weight based on the total weight of the polymer. Higher α-olefins refer to α-olefins having three or more carbon atoms.

[0043] Polyolefins include polymers prepared from olefin monomers such as ethylene, namely polyethylene and polymers prepared from linear or branched higher alpha-olefin monomers containing 3 to 20 carbon atoms. Examples of higher alpha-olefin monomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 3,5,5-trimethyl-1-hexene. Examples of polyolefins include ethylene-based polymers having at least 50 weight% ethylene, particularly ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene copolymers. Other olefins that may be used include, for example, ethylene-based unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cyclic olefins. Examples of monomers may include, but are not limited to, norbornene, norbornene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentene. In many embodiments, copolymers of ethylene may be prepared, and 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 may be polymerized with at least two different comonomers to produce a terpolymer, and optionally, one of the comonomers may be a diene.

[0044] One or more embodiments provide that the polymer may comprise units derived from ethylene in an amount of 1 to 100 weight% based on the total weight of the polymer. All individual values ​​and sub-ranges of 1 to 100 weight% are included; for example, the polymer may comprise units derived from ethylene in an upper limit of 100, 99, 95, 90, or 85 weight% based on the total weight of the polymer.

[0045] As mentioned, surprisingly, a polymerization catalyst prepared from the titanium biphenylphenol polymerization precatalyst of Formula I can have a desirable (lower) productivity compared to a polymer prepared with other polymerization catalysts under similar polymerization conditions. For example, a polymerization catalyst prepared from the titanium biphenylphenol polymerization precatalyst of Formula I has a productivity (gPE / gcatalyst / hour) in the range of 35 to 5,000,000 gPE / gcatalyst / hour. All individual values ​​and sub-ranges of 35 to 5,000,000 gPE / gcatalyst+activator / hour are included. For example, productivity may 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 the polymerization of both occurs at the same polymerization temperature and conditions, e.g., the same hydrogen concentration and / or the same comonomer-to-monomer ratio, compared to a polymer produced with a different polymerization catalyst. While not intended to be bound by theory, lower productivity is believed to preferably reduce reactor fouling due to thermal excursion and / or reduce catalyst decomposition, or / or improve operability compared to a catalyst with higher productivity under similar conditions, which could otherwise lead to operability problems in a gas-phase polymerization reactor.

[0046] Furthermore, as mentioned, surprisingly, the titanium biphenylphenol polymerization precatalyst of Formula I can help provide a polymer having an improved, i.e., lower molecular weight, compared to a polymer prepared with another polymerization catalyst under similar polymerization conditions. For example, the titanium biphenylphenol polymerization catalyst of the present disclosure can help provide a polymer having a reduced molecular weight compared to a polymer prepared with another polymerization catalyst when the polymerization of both occurs at the same polymerization temperature and conditions, e.g., the same hydrogen concentration and / or the same comonomer-to-monomer ratio. Embodiments provide that the polymer may have a weight average molecular weight (Mw) of 60,000 to 350,000. All individual values ​​and sub-ranges of 60,000 to 350,000 are included; for example, the polymer may be 60,000; 100,000; It may have an Mw of a lower limit of 102,000 or 105,000 to 350,000, 336,000; 286,000; 273,000; 203,000; or an upper limit of 110,000. Mw may be determined by the GPC described below. Although not intended to be bound by theory, polymers with lower molecular weights are considered to be easier to process than polymers with higher molecular weights due to their lower viscosity in the molten phase.

[0047] The embodiments provide that the polymer may have a melt index (I2) measured by D1238 (190°C, 2.16 kg load) in the range of 0.001 g / 10 min to 1000 g / 10 min. All individual values ​​and sub-ranges of 0.001 g / 10 min to 1000 g / 10 min are included. For example, the polymer may have a melt index of 0.001 g / 10 min to 1000 g / 10 min 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.

[0048] The embodiment provides that the polymer may have a melt index (I5) measured by D1238 (190°C, 5 kg load) in the range of 0.001 g / 10 min to 1000 g / 10 min. All individual values ​​and sub-ranges of 0.001 g / 10 min to 1000 g / 10 min are included. For example, the polymer may have a melt index (I5) of 0.02 g / 10 min to 5 g / 10 min.

[0049] The embodiment is a melt index (I) of the polymer measured by D1238 (190°C, 21 kg load) in the range of 0.001 g / 10 min to 1000 g / 10 min. 21 It provides that it may have ). All individual values ​​and sub-ranges from 0.001 g / 10 min to 1000 g / 10 min are included. For example, the polymer has a melt index (I) of 0.001 g / 10 min to 53 g / 10 min. 21 Can have ).

[0050] The embodiments provide that the polymer may have a number average molecular weight (Mn) of 5,000 to 98,000. All individual values ​​and sub-ranges of 5,000 to 98,000 are included; for example, the polymer may have a lower limit of 5,000; 6,000; 16,000; or 28,000 and a higher limit of 98,000; 75,000; 69,000; 55,000; 45,000; or 35,000. Mn may be determined by gel permeation chromatography (GPC) known in the art.

[0051] The embodiments provide that the polymer may have a molecular weight distribution determined as Mw / Mn (weight average molecular weight / number average molecular weight) of 2.90 to 21.00. All individual values ​​and sub-ranges of 2.90 to 21.00 are included; for example, the polymer may have Mw / Mn of a lower limit of 2.90; 3.00; 3.50; 4.00; or 4.50; 21.00; 20.00; 8.00; 7.50; 7.00; or 6.50. In some embodiments, Mw / Mn may be in the range of 2.90 to about 4.00. Mw / Mn may be determined by GPC analysis as described below.

[0052] The embodiments provide that the polymer may have a melting temperature of 100 to 165°C. All individual values ​​and sub-ranges of 100 to 165°C are included; for example, the polymer may have a melting temperature of 100, 105, or 110°C at a lower limit and 165, 160, or 155°C at an upper limit. The melting temperature may be determined by differential scanning calorimetry according to ASTM D 3418-08.

[0053] The embodiment is 0.890 g / cm³ 3 Up to 0.970 g / cm³ 3 It provides a density that can have a density of 0.890 to 0.970 g / cm³ 3 All individual values ​​and sub-ranges are included; for example, the polymer is 0.890, 0.900, 0.910, or 0.920 g / cm³ 3 The lower limit of 0.970, 0.960, 0.950, or 0.940 g / cm³ 3 It can have an upper limit density. The density is ASTM D-792-13 (for testing solid plastics in liquids other than water, e.g., liquid 2-propanol), Standard test method for the density and specific gravity (relative density) of plastics due to displacement , can be determined according to Method B. The result is in grams per cubic centimeter (g / cm²). 3 It is represented as ).

[0054] Gel Permeation Chromatography (GPC) Test Method: Weight Average Molecular Weight Test Method: Using the chromatogram obtained from a High Temperature Gel Permeation Chromatography instrument (HTGPC, Polymer Laboratories), M w , number average molecular weight (M n ) and M w / M n Determine the following. The HTGPC is equipped with a transfer line, a differential refractive index (DRI) detector, and three Polymer Laboratories PL-gel 10 μm Mixed-B columns, all of which are held in an oven maintained at 160°C. The method uses a solvent composed of BHT-treated TCB at a nominal flow rate of 1.0 ml / min (mL / min) and a nominal injection volume of 300 microliters (μL). The solvent is prepared by dissolving 6 g of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent-grade 1,2,4-trichlorobenzene (TCB) and filtering the resulting solution through a 0.1 micrometer (μm) Teflon filter to provide the solvent. The solvent is degassed using an inline degasser before being introduced into the HTGPC instrument. The columns are calibrated with a series of monodisperse polystyrene (PS) standards. Separately, a test polymer at a known concentration dissolved in a solvent is prepared by heating a known amount of the test polymer in a known volume of solvent at 160°C for 2 hours while continuously shaking to provide a solution. (All amounts are measured by gravimetric measurement.) Solution concentration of the test polymer at 0.5 to 2.0 milligrams of polymer (mg / mL) per milliliter of solution. cThe goal is to, and a lower concentration c is used for polymers with higher molecular weights. Before running each sample, the DRI detector is purged. Subsequently, the flow rate within the device is increased to 1.0 mL / min, and the DRI detector is allowed to stabilize for 8 hours before injecting the first sample. Using column calibration and general calibration relationships, M w and M n Calculate . Calculate MW at each elution volume using the following formula: , in the above formula, the subscript "X" represents a test sample, and the subscript "PS" represents a PS standard, , And, and It is obtained from published literature. In the case of polyethylene, a x / K x = 0.695 / 0.000579. In the case of polypropylene, a x / K x = 0.705 / 0.0002288. At each point in the obtained chromatogram, the baseline subtracted DRI signal I is calculated using the following equation. DRI concentration from c Calculating: c = K DRI I DRI / (dn / dc), in the above formula, K DRI is a constant determined by DRI correction, / indicates division, and dn / dc is the increment of the refractive index for the polymer. For polyethylene, dn / dc = 0.109. The mass recovery rate of the polymer is calculated from the ratio of the integrated area of ​​the concentration chromatography chromatogram to the injection mass and elution volume equal to the predetermined concentration multiplied by the injection loop volume. Unless otherwise noted, all molecular weights are reported in grams / mol (g / mol). Further details regarding the method for determining Mw, Mn, and MWD are described in U.S. Patent Application Publication US 2006 / 0173123, pages 24 to 25, paragraphs

[0334] to

[0341] . A GPC chromatogram is provided by plotting dW / dLog(MW) on the y-axis versus Log(MW) on the x-axis, where Log(MW) and dW / dLog(MW) are as defined above.

[0055] Polymers can be used in a number of articles, particularly films, fibers, nonwovens and / or fabrics, extruded articles, and / or molded articles.

[0056] A bimodal catalyst system is also provided, comprising a titanium biphenylphenol polymerization precatalyst of Formula I or an activation reaction product thereof, and at least one olefin polymerization catalyst (second catalyst) that is not the titanium biphenylphenol polymerization precatalyst of Formula I or an activation reaction product thereof. This second catalyst may be a Ziegler-Natta catalyst, a chromium-based catalyst (e.g., the so-called Phillips catalyst), a metallocene catalyst without or containing an indenyl ring (e.g., a metallocene catalyst containing an unsubstituted and / or alkyl-substituted cyclopentadienyl ring), a Group 15 metal-containing catalyst compound described in paragraphs

[0041] to

[0046] of International Publication WO 2018 / 064038 A1, or a biphenylphenol-based catalyst compound described in paragraphs

[0036] to

[0080] of U.S. Patent Application Publication US 20180002464A1.

[0057] In addition to the titanium biphenylphenol polymerization precatalyst of Formula I, other components discussed herein, such as activators and / or additional polymerization components, may be used as supports. The term "support," which may also be referred to as a carrier, refers to any support material comprising porous support materials such as talc, inorganic oxides, and inorganic chlorides.

[0058] The titanium biphenylphenol polymerization precatalyst of Formula I, as well as other components discussed herein, may be supported on the same or separate supports, or one or more components may be used in an unsupported form. The use of a support 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 support may be functionalized.

[0059] The support may be a porous support material, for example, talc, inorganic oxide, or inorganic chloride. Other support materials include resinous support materials, for example, polystyrene; functionalized or cross-linked organic supports, for example, polystyrene divinylbenzene polyolefin or polymer compounds; zeolites; clay; or any other organic or inorganic support material, or mixtures thereof.

[0060] The support material comprises an inorganic oxide containing a metal oxide of Group 2, 3, 4, 5, 13, or 14. Some preferred supports include silica, fumed silica, alumina, silica-alumina, and mixtures thereof. Some other supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phylosilicate, zeolite, talc, clay, etc. Additionally, combinations of these support materials, for example, silica-chromium, silica-alumina, silica-titania, etc., may be used. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads.

[0061] Examples of supports include fumed silica available under the trade name Cabosil™ TS-610 from Cabot Corporation, or other TS- or TG-series supports. Fumed silica is silica having particles 7 to 30 nanometers in size, typically treated with dimethylsilyl dichloride so that most surface hydroxyl groups are capped.

[0062] The support material has a surface area in the range of about 10 to about 700 m / g and about 0.1 to about 4.0 g / cm². 3 It may have a pore volume in the range and an average particle size in the range of about 5 to about 500 μm. More preferably, the surface area of ​​the support material is in the range of about 50 to about 500 m / g, and the pore volume is about 0.5 to about 3.5 g / cm³. 3 And, the average particle size is about 10 to about 200 μm. Most preferably, the surface area of ​​the support material is in the range of about 100 to about 400 m / g, and the pore volume is about 0.8 to about 3.0 g / cm³. 3The average particle size is about 5 to about 100 μm. The average pore size of the carrier typically has a pore size in the range of 10 to 1000 A, preferably 50 to about 500 A, and most preferably 75 to about 350 A.

[0063] The molar ratio of the metal in the activator to the metal in the titanium biphenylphenol polymerization precatalyst of Formula I may be 1000:1 to 0.5:1, 300:1 to 1:1, or 150:1 to 1:1. One or more diluents, for example, fluids, may be used to facilitate the combination of any two or more components. For example, the titanium biphenylphenol polymerization precatalyst of Formula I and the activator may be combined together in the presence of toluene or other non-reactive hydrocarbons or hydrocarbon mixtures. In addition to toluene, other suitable diluents may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. Subsequently, a dry or toluene-mixed support may be added to the mixture, or the titanium biphenylphenol polymerization catalyst / activator may be added to the support. The slurry can be supplied to a reactor for a polymerization process and / or the slurry can be dried, for example, spray-dried, before being supplied to a reactor for a polymerization process.

[0064] The polymerization process may utilize known equipment and reaction conditions, for example, known polymerization conditions. The polymerization process is not limited to any specific type of polymerization system. For example, the polymerization temperature may be in the range of about 0°C to about 300°C at atmospheric pressure, below atmospheric pressure, or super-atmospheric pressure. The embodiments provide a method for producing a polyolefin polymer, the method comprising the step of producing a polyolefin polymer by polymerizing the olefin by contacting the olefin with the titanium biphenylphenol polymerization catalyst described herein under polymerization conditions.

[0065] One or more embodiments provide that the polymer can be produced through a gas phase polymerization system at a superatmosphere 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 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. In one or more embodiments, the temperature may be 80°C, 90°C, or 100°C. A stirred and / or fluidized bed gas phase polymerization system may be used.

[0066] 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 layer of solid particles in a suspension, in the presence of a catalytic composition, for example, an activated titanium biphenylphenol polymerization precatalyst of Formula I, and under reaction conditions. The stream containing unreacted monomers can be continuously recovered from the reactor, compressed, cooled, optionally partially or completely condensed, and recirculated back to the reactor. The product, i.e., the polymer, can be recovered from the reactor, and a replacement monomer can be added to the recirculated stream. A gas inert to the catalytic composition and the reactants may also be present in the gas stream. The polymerization system may include, for example, a single reactor or two or more reactors in series.

[0067] The feed stream for the polymerization process may include olefin monomers, non-olefin gases, e.g., nitrogen and / or hydrogen, and may further include one or more non-reactive alkanes that can be condensed in the polymerization process and used to remove the heat of reaction. Exemplary non-reactive alkanes include, butane, isobutane, pentane, isopentane, hexane, isomers thereof, and derivatives thereof, but are not limited thereto. The feed may be introduced into the reactor at a single or multiple and different locations.

[0068] For the polymerization process, the polymerization catalyst can be continuously supplied to the reactor. The polymerization catalyst can be transported into the reactor bed using a gas inert to the polymerization catalyst, for example, nitrogen or argon.

[0069] In one embodiment, the polymerization catalyst may be provided as a slurry in a mineral oil or liquid hydrocarbon or mixture, such as propane, butane, isopentane, hexane, heptane, or octane. The slurry may be delivered to a reactor together with a carrier fluid, such as nitrogen or argon, or a liquid, such as isopentane or other C3 to C8 alkanes.

[0070] For the polymerization process, hydrogen may be used in a gas molar ratio of hydrogen to ethylene in the reactor, which may be in the range of about 0.0 to 1.0, 0.01 to 0.7, 0.03 to 0.5, or 0.005 to 0.4. Many embodiments use hydrogen gas. In some embodiments, the gas molar ratio of hydrogen to ethylene in the reactor may be 0.0068, 0.0016, or 0.0011.

[0071] Many embodiments of the present disclosure are provided as follows.

[0072] Embodiment 1 provides a titanium biphenylphenol polymerization precursor of Formula I:

[0073]

[0074] In the above equation, R 7 and R 8 Each independently C1 to C 20 alkyl, aryl, aralkyl, or hydrogen; R 5 and R 10 Each independently C1 to C 20 It is an alkyl, aryl, aralkyl, halide, or hydrogen; R 2 and R 13 Each independently C1 to C 20 alkyl, aryl, aralkyl, or hydrogen; R 15 and R 16 is each 2,7-disubstituted carbozol-9-yl or 3,6-disubstituted-carbozol-9-yl; L is a C2-C4 alkylene that forms a 2-carbon bridge, a 3-carbon bridge, or a 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded; and R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 Each is independently a halide or hydrogen; each X is independently a hydrocarbyl, halide, pseudo-halide, hydroxyl group, alkoxy group, phenoxy group, aryloxy group, or hydrogen, and at least one X is not hydrocarbyl.

[0075] Mode 2 is R 7 and R 8 Each of these is C1alkyl or R 7 and R 8 Each of these provides a titanium biphenylphenol polymerization precursor of the chemical formula I of embodiment 1, which is hydrogen.

[0076] Mode 3 is R 5 and R 10 Each provides a titanium biphenylphenol polymerization precursor catalyst of Formula I of Embodiment 1 or Embodiment 2, which is a dialkyl or trialkyl substituted silyl.

[0077] Mode 4 is R 5 and R 10 Each of these provides a titanium biphenylphenol polymerization precursor of Formula I of Embodiment 1, which is octyl dimethyl silyl.

[0078] Modality 5 is R 5 and R 10 Each provides a titanium biphenylphenol polymerization precursor catalyst of Formula I of Embodiment 1 or Embodiment 2, which is fluorine.

[0079] Modality 6 is R 2 and R 13 Each of the titanium biphenylphenol polymerization precursors of Formula I in any one of embodiments 1 to 5 is 1,1-dimethylethyl.

[0080] Modality 7 is R 15 and R 16 This provides a titanium biphenylphenol polymerization precursor catalyst of Formula I in any one of embodiments 1 to 6, each being 2,7-di-t-butylcarbazole-9-yl or 3,6-di-t-butylcarbazole-9-yl.

[0081] Embodiment 8 provides a titanium biphenylphenol polymerization precursor of Formula I of any one of Embodiments 1 to 7, in which L is a saturated C3-alkylene.

[0082] Embodiment 9 provides a titanium biphenylphenol polymerization precursor of Formula I of any one of Embodiments 1 to 8, in which each X is chlorine.

[0083] Embodiment 10 further comprises a silica support without an activator, and provides a titanium biphenylphenol polymerization precatalyst of Formula I of any one of Embodiments 1 to 9, wherein the activator-free silica support supports the precatalyst.

[0084] Embodiment 11 provides a method for preparing a titanium biphenylphenol polymerization catalyst, the method comprising the step of preparing a titanium biphenylphenol polymerization catalyst by contacting a titanium biphenylphenol polymerization precursor catalyst of Formula 1 of any one of Embodiments 1 to 10 with an activating agent under activation conditions to activate the titanium biphenylphenol polymerization precursor catalyst of Formula 1.

[0085] Embodiment 12 provides a method for preparing a titanium biphenylphenol polymerization catalyst of Embodiment 11, and further comprises the step of preparing a titanium biphenylphenol polymerization catalyst on a silica support by contacting a non-activating agent solution of a titanium biphenylphenol polymerization precursor of Formula I dissolved in an alkane solvent with a silica support containing an activating agent spray-dried on top.

[0086] Embodiment 13 provides a titanium biphenylphenol polymerization catalyst prepared by the method of preparing the titanium biphenylphenol polymerization catalyst of Embodiment 11 or Embodiment 12.

[0087] Embodiment 14 provides a method for manufacturing polyethylene, the method comprising the step of polymerizing olefin monomers in a single-phase polymerization reactor in the presence of the titanium biphenylphenol polymerization catalyst of Embodiment 13 to produce a polyethylene composition.

[0088] Embodiment 15 provides a method for producing polyethylene of Embodiment 14, further comprising the step of preparing a titanium biphenylphenol polymerization catalyst before the polymerization step; and the step of feeding the titanium biphenyl polymerization catalyst to a single-phase polymerization reactor.

[0089] Examples

[0090] A titanium biphenylphenol polymerization precursor of formula (i) is prepared as follows. In a glove box, a 40 ml (mL) oven-dried glass vial is filled with the ligand of formula A (0.500 g, 0.407 mmol), diethyl ether [Et2O] (20 mL; available from Fisher Scientific) and a magnetic stirring bar. The ligand of formula A (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol) was prepared as described in International Publication WO 2012 / 027,448, the entire contents of which are incorporated herein by reference. The contents of the vial were stirred until the ligand of formula A was dissolved, and then the contents of the vial were cooled to approximately -30°C. Subsequently, 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. An immediate color change to deep red was observed, and the mixture was then stirred overnight at room temperature. The solvent The residue was removed under vacuum, suspended in cooled pentane, and then filtered to obtain a red solid washed with pentane (0.55 g, 100% yield). The presence of the titanium biphenylphenol polymerization precatalyst of formula i 1 It was confirmed by H NMR analysis. 11H NMR (400 MHz, C6D6) δ 8.60 (d, J = 1.9 Hz, 2H), 8.40 (d, J = 1.9 Hz, 2H), 7.77 - 7.57 (m, 6H), 7.49 (d, J = 2.4 Hz, 2H), 7.40 (d, J = 8.6 Hz, 2H), 7.22 (d, J = 2.4 Hz, 2H), 6.91 (dd, J = 8.5, 3.2 Hz, 2H), 6.18 - 6.03 (m, 2H), 5.78 (dd, J = 9.4, 4.5 Hz, 2H), 3.86 (d, J = 8.2 Hz, 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 (101 MHz, C6D6) δ 214.97, 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 (376 MHz, C6D6) δ -122.45.

[0091]

[0092] The titanium biphenylphenol polymerization precatalyst of formula (ii) was prepared using the same components and methodology as the titanium biphenylphenol polymerization precatalyst of formula i, but with the ligand of formula B (0.500 g, 0.398 mmol) 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-carbazole-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[l,l'-biphenyl]-2-ol) was prepared as described in International Publication WO 2014 / 105411, the entire contents of which are incorporated herein by reference. The presence of the titanium biphenylphenol polymerization precatalyst of formula (ii) 1 It was confirmed by H NMR analysis. 1 H NMR (400 MHz, C6D6) 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). 13C NMR (101 MHz, C6D6) δ 161.92, 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.

[0093]

[0094] The titanium biphenylphenol polymerization precatalyst of formula (iii) was prepared using the same components and methodology as the titanium biphenylphenol polymerization precatalyst of formula i, except that the ligand of formula C (4.000 g, 2.563 mmol) and pentane (available from Sigma Aldrich) were used as the solvent instead of the ligand of formula A (1.098 g, 26% yield). The ligand of formula C was prepared as described in International Publication WO 2017 / 058,981, the full contents of which are incorporated herein by reference. The presence of the titanium biphenylphenol polymerization precatalyst of formula (iii) 1 It was confirmed by H NMR analysis. 1H NMR (400 MHz, C6D6) 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 (H-5), J = 2.2 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 = 1.H06, 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), 1.627 (s, - 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, C6D6) with δ 158.73, 157.86, 150.50, 131.53, 129.05, 127.37, 126.34, 124.74, 119.91, 119.87, 118.26, 110.29, 3.758.71, 35.82, 34.40, 33.37, 32.75, 32.71, 32.39, 32.10, 30.31, 30.14, 30.12, 29.78, 24.71, 23.47, 16.88, −2.66, −2.75.

[0095]

[0096] As used herein, "Me" refers to methyl, and "t-Bu" refers to tert-butyl.

[0097] Comparative polymerization precatalysts of formulas (iv) and (v) were prepared as described in International Publication WO 2017 / 058981 A1, the entire contents of International Publication WO 2017 / 058981 A1 incorporated herein by reference.

[0098]

[0099]

[0100] The activation of titanium biphenylphenol polymerization precatalysts of chemical formulas i, ii, iii, iv, and v was carried out by Method I or Method II, which are described in detail below.

[0101] Method I:

[0102] Example 1 (EX1), an activated titanium biphenylphenol polymerization catalyst of Formula I was prepared according to Method I below. In a nitrogen-purged glove box, an oven-dried glass vial was filled with 2.65 g (g) of treated fumed silica (CABOSIL TS-610; available from WR Grace) slurried in 75 g of toluene (available from Aldrich) and stirred until well dispersed. 22 g of a 10 wt% methylaluminoxan (MAO) solution (available from WR Grace as 10 wt% in toluene) was added to the vial to form a mixture. After stirring the mixture by magnetism for 15 minutes, 0.303 g of the titanium biphenylphenol polymerization catalyst of Formula III was added, and the mixture was stirred for 30 to 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), suction - 95, and pump speed - 150 rpm.

[0103] Example 2 (EX2) was prepared in the same manner as Example 1, but with the catalyst of Example 2 shown in Table 1 used.

[0104] Example 3 (EX3) was prepared in the same manner as Example 1, but with the catalyst of Example 3 shown in Table 1 used.

[0105] Method II:

[0106] The activated titanium biphenylphenol polymerization catalyst of Formula I in Examples 4 to 11 (EX4-11) and the catalyst of Comparative Examples 1 to 7 (CE1-7) were prepared according to Method II below.

[0107] For Example 4, 0.9 mg / mL of a suspension of the titanium biphenylphenol polymerization precursor 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 into a bomb-containing activator in the form of spray-dried methylaluminoxane in the amount shown in Table 1 (e.g., 0.0015 g) as a non-activator solution to prepare the activated and supported titanium biphenylphenol polymerization catalyst of Example 4.

[0108] The activated titanium biphenylphenol polymerization catalysts of Examples 5 to 11 were prepared as in Example 4, but modified to use each catalyst and the amount of catalyst listed in Table 1 for Examples 5 to 11.

[0109] The activation catalysts of Comparative Examples 1 to 7 were prepared as in Example 4, but the respective catalysts and amounts of catalysts of Comparative Examples 1 to 7 listed in Table 1 were used.

[0110] Titanium

[0111] The ethylene / 1-hexene copolymerization of Examples 1 to 11 and Comparative Examples 1 to 7 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, 200 g of sodium chloride (NaCl) was charged, and the mixture was dried by heating at 100°C under nitrogen for 30 minutes. 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. Subsequently, the reactor was charged with hydrogen (H2 preloading amount for each condition as described below) and hexene (C6 / C2 ratio for each condition as described below) and pressurized with ethylene (230 psi). Once the system reached a steady state, polymerization was initiated by loading the type and amount of each activation catalyst (activated via Method I or II) identified in Table 1 into the reactor at 80°C for each of Examples 1 to 11 and Comparative Examples 1 to 7. The reactor temperature was raised to 90 to 100°C and maintained at this temperature throughout the 1-hour run. The run was carried out under conditions 1, 2, 3, or 4 identified in Table 1 and described in detail below. 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 Examples 1 to 11 and Comparative Examples 1 to 7 are presented in Table 2.

[0112] Productivity (g polymer / g catalyst / time) was determined as the ratio of the polymer produced to the amounts of catalyst and activator added to the reactor.

[0113] 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) are determined by gel permeation chromatography (GPC) known in the art.

[0114] The content of the comonomer incorporated into the polymer (i.e., 1-hexene) was determined by rapid FT-IR spectroscopy of the dissolved polymer in GPC measurements.

[0115] The melt index (MI, I2) can be measured according to ASTM D1238 (190°C, 2.16 kg weight). The melt index (MI, I5) can be measured according to ASTM D1238 (190°C, 5 kg). The melt index (MI, I 21 ) can be measured according to ASTM D1238 (190℃, 21.6 kg).

[0116] Condition 1: C6 / C2 ratio = 0.004, H2 preload = 5.02 liters (L), H2 / C2 ratio = 0.0068, C2 pressure = 230 square inches / pound (psi); Condition 2: C6 / C2 ratio = 0.004, H2 preload = 1.18 L, H2 / C2 ratio = 0.0016, C2 pressure = 230 psi; Condition 3: C6 / C2 ratio = 0.016, H2 preload = 0.81 L, H2 / C2 ratio = 0.0011, C2 pressure = 230 psi; Condition 4: C6 / C2 ratio = 0.016, H2 preload = 0.40 L, H2 / C2 = 0.0011, C2 pressure = 115 psi.

[0117]

[0118]

[0119] As described in detail in Tables 1 and 2, Examples 1 to 11 provide a titanium biphenylphenol polymerization catalyst and a obtained polymer having suitable properties.

[0120] The titanium biphenylphenol polymerization catalyst of the present disclosure can produce polymers with lower molecular weights than polymers from comparative catalysts. For example, under Condition 1 and Catalyst Addition Method II, Comparative Examples 1 and 2 have molecular weights of 259,109 and 202,837, respectively, compared to molecular weights of 105,215 and 102,243, respectively, of Examples 4 and 5. That is, the molecular weight of the polymer obtained from the titanium biphenylphenol polymerization catalyst of the present disclosure is at least 40% lower than the molecular weight of the comparative polymer, and the titanium biphenylphenol polymerization catalyst still possesses other desired characteristics (Mn, Mz, Mw / Mn ratio, comonomer incorporation %, I2, I5, I 21, Provides yield, and / or productivity.

[0121] For example, the titanium biphenylphenol polymerization catalyst of the present disclosure may have lower productivity than the comparative catalyst. As detailed in Table 1, Examples 4 to 11 all have lower productivity than Comparative Examples 1 to 7. While not intended to be bound by theory, lower productivity is believed to preferably reduce catalyst degradation and / or improve operability compared to catalysts with higher productivity, which could otherwise lead to operability problems in the gas-phase polymerization reactor.

[0122] Additionally, Examples 4 through 11 demonstrate that the operability of the titanium biphenylphenol polymerization catalyst of the present disclosure can be improved by using Catalyst Addition Method II instead of Catalyst Addition Method I. Under Conditions 1 and 2, Examples 4 through 11 (Method II) provide higher yields and / or productivity than when the same or similar titanium catalyst is used in Method I (Examples 1 through 3). While not intended to be bound by theory, using Method II is believed to mitigate catalyst degradation compared to other approaches (e.g., conventional supported / slurry) such as Method I, which prepare an activated catalyst by contacting the procatalyst and activator in the mixture before spray drying, thereby allowing a significant amount of time for the catalyst to decompose once formed. In other words, Examples 4 through 11 using Method II prepare an activated catalyst using a solution that is non-activating (absence of any activating agent) until it is subsequently contacted with an activating agent, such as a spray-dried activating agent, and the catalyst is then fed directly / immediately into a gas-phase polymerization reactor (e.g., as a trim catalyst) to reduce any catalyst degradation and thus improve operability. For example, the catalyst may be fed directly into the gas-phase polymerization reactor via inline trim addition or other mechanisms immediately after forming the activated titanium biphenylphenol polymerization catalyst through Method II described herein.

[0123] The titanium biphenylphenol polymerization catalyst of the present disclosure preferably incorporates less comonomer (1-hexene). For example, under condition 3, Comparative Examples 4 and 5 have comonomer incorporation of 5.35% and 6.14%, respectively, compared to the comonomer incorporation of 2.98% and 3.07%, respectively, of Examples 8 and 9. That is, the comonomer incorporation of the polymer obtained from the titanium biphenylphenol polymerization catalyst of the present disclosure may be at least 65% less than the comonomer incorporation of the comparative catalyst used under the same conditions (conditions 2, 3, and 4) and catalytic method.

Claims

Claim 1 As a titanium biphenylphenol polymerization precursor catalyst of chemical formula I, In the above equation, R 7 and R 8 Each independently C1 to C 20 alkyl, aryl, aralkyl, or hydrogen; R 5 and R 10 are each independently a dialkyl or trialkyl substituted silyl; R 2 and R 13 Each independently C1 to C 20 alkyl, aryl, aralkyl, or hydrogen; R 15 and R 16 are each a 2,7-disubstituted carbazole or a 3,6-disubstituted carbazole; L is a C2-C4 alkylene that forms a 2-carbon bridge, a 3-carbon bridge, or a 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded; and R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 Each is independently a halide or hydrogen; each X is independently a hydrocarbyl, halide, pseudo-halide, hydroxyl group, alkoxy group, phenoxy group, aryloxy group, or hydrogen, and at least one X is not a hydrocarbyl, titanium biphenylphenol polymerization precatalyst. Claim 2 In paragraph 1, R 7 and R 8 are each C1alkyl or R 7 and R 8 Titanium biphenylphenol polymerization precursor catalysts, each containing hydrogen. Claim 3 In paragraph 1 or 2, R 5 and R 10 Titanium biphenylphenol polymerization precursor catalysts, each being octyl dimethyl silyl. Claim 4 In paragraph 1 or 2, R 2 and R 13 Titanium biphenylphenol polymerization precursor catalysts, each being 1,1-dimethylethyl. Claim 5 In paragraph 1 or 2, R 15 and R 16 Titanium biphenylphenol polymerization precursor catalysts, each being 2,7-di-t-butylcarbazole or 3,6-di-t-butylcarbazole. Claim 6 A titanium biphenylphenol polymerization precursor catalyst, wherein L is a saturated C3-alkylene, in claim 1 or 2. Claim 7 A titanium biphenylphenol polymerization precursor catalyst, wherein each X is chlorine, in paragraph 1 or 2. Claim 8 A titanium biphenylphenol polymerization precursor according to claim 1 or 2, further comprising a silica support without an activator, wherein the activator-free silica support supports the precursor catalyst. Claim 9 A method for preparing a titanium biphenylphenol polymerization catalyst, comprising the step of preparing a titanium biphenylphenol polymerization catalyst by activating the titanium biphenylphenol polymerization precursor catalyst of Formula I of Claim 1 or 2 by contacting it with an activating agent under activation conditions. Claim 10 A method for preparing a titanium biphenylphenol polymerization catalyst according to claim 9, further comprising the step of preparing a titanium biphenylphenol polymerization catalyst on a silica support by contacting a non-activating agent solution of a titanium biphenylphenol polymerization precatalyst of formula I dissolved in an alkane solvent with a silica support containing a spray-dried activating agent on the support. Claim 11 A method for manufacturing a polyethylene composition, comprising the step of manufacturing a polyethylene composition by polymerizing an olefin monomer containing an ethylene monomer in a single-phase polymerization reactor in the presence of a titanium biphenylphenol polymerization catalyst manufactured by the method of claim 9. Claim 12 A method for preparing a polyethylene composition according to claim 11, further comprising the steps of: preparing a titanium biphenylphenol polymerization catalyst before the step of polymerizing an olefin monomer including an ethylene monomer; and supplying the titanium biphenylphenol polymerization catalyst into a single-phase polymerization reactor. Claim 13 delete Claim 14 delete Claim 15 delete

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