Spray-dried compositions including a hafnium phenol-oxadiazole complex

Abstract

Embodiments of the present disclosure are directed towards spray-dried compositions including a Hf phenol-oxadiazole complex and methods utilizing these spray-dried compositions.

Description

SPRAY-DRIED COMPOSITIONS INCLUDING A HAFNIUM PHENOL-OXADIAZOLE COMPLEXField of Disclosure

[0001] Embodiments of the present disclosure are directed towards spray-dried compositions including a hafnium (Hf) phenol-oxadiazole complex, and methods utilizing a spray-dried composition including a Hf phenol-oxadiazole complex.Background

[0002] Polymers may be utilized for a number of products including films, fibers, pipes, nonwoven and / or woven fabrics, extruded articles, and / or molded articles, among others. Polymers can be formed by reacting one or more types of monomer in a polymerization reaction. There is continued focus in the industry on developing new and improved materials and / or processes that may be utilized to form polymers.Summary

[0003] The present disclosure provides various embodiments, including the following.

[0004] A spray-dried composition comprising: a Hf phenol-oxadiazole complex represented by structure (I):structure (I) wherein each Ar is 2,6-Cl2Ph, R1 -R6 are each independently H, a C1 -C20 alkyl, fluorine (F), or trifluoromethyl (CF3), and each X is a leaving group; an activator; and a support.

[0005] A method for providing polyolefins having long chain branching via a gas phase polymerization, the method including contacting the spray-dried composition and an olefin under polymerization conditions within a gas-phase reactor to make the polyolefins.Detailed Description

[0006] Spray-dried compositions, e.g., catalyst systems, including a Hf phenoloxadiazole complex are disclosed herein. These compositions can be utilized to make polyolefins in gas phase polymerizations. Advantageously, these compositions can be utilized to make polyolefins having long chain branching via gas phase polymerizations, as indicated by as indicated by13C NMR and / or Mark-Houwink plotting. Long chain branching is generally not observed in polyolefins made via gas phase polymerizations.

[0007] Additionally, advantageously, the polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can have an advantageous polydispersity index (Mw / Mn) from 1.5 to 6.0. This decreased and / or narrowed, polydispersity index, as compared to other compositions made with a number of other catalysts, can provide more catalyst and / or polyethylene resin design degrees of freedom along and / or enhanced polyethylene product performance.

[0008] The spray-dried compositions disclosed herein include a Hf phenol- oxadiazole complex. The Hf phenol-oxadiazole complex can be represented by structure (I):structure (I)

[0009] wherein each Ar is 2,6-Cl2Ph; R^ -R® are each independently H, a Cf - C20 alkyl, fluorine (F), or trifluoromethyl (CF3); and each X is a leaving group.

[0010] Phenol-oxadiazole complexes are known. The Hf phenol-oxadiazole complexes represented by structure (I) can be made by processes, i.e. with conventional solvents, reaction conditions, reaction times, and isolation procedures, utilized for making known phenol-oxadiazole complexes. A number of the Hf phenol-oxadiazole complex represented by structure (I) can be obtained by various providers.

[0011] As mentioned, each X is independently a leaving group. Each X can independently selected from fluoride, chloride, bromide, methyl, ethyl, phenyl, benzyl,phenyloxy, benzloxy, 2-phenyl-2-propoxy, 1-phenyl-2-propoxy, 1 -phenyl-2-butoxy, and 2-phenyl-2-butoxy. One or more embodiments provide X is benzyl or chloride.

[0012] One or more embodiments provide that R3and R6are each a C4 alkyl, R1, R2, R4, and R5are each H, and each X is benzyl (Bn), where the Hf phenoloxadiazole complex can be represented by structure (II):structure (II).

[0013] As shown by structure (III), the C4 alkyl can be t-butyl, for instance.

[0014] One or more embodiments provide that R1and R3are each F, R6is a C4 alkyl, R2, R4, and R5are each H, and each X is benzyl (Bn), where the Hf phenoloxadiazole complex can be represented by structure (III):structure (III).

[0015] One or more embodiments provide that R1and R4are each F, R6is a C4 alkyl, R2, R3, and R5are each H, and each X is benzyl (Bn), where the Hf phenoloxadiazole complex can be represented by structure (IV):structure (IV).

[0016] One or more embodiments provide that R3is F, R6is a C4 alkyl, R1, R2, R4, and R5are each H, and each X is benzyl (Bn), where the Hf phenol-oxadiazole complex can be represented by structure (V):structure (V).

[0017] One or more embodiments provide that R2and R4are each a C1 alkyl (methyl), R6is a C4 alkyl, R1, R3, and R5are each H, and each X is benzyl (Bn), where the Hf phenol-oxadiazole complex can be represented by structure (VI):structure (VI).

[0018] One or more embodiments provide that R3is trifluoromethyl, R6is a C4 alkyl, R1, R2, R4, and R5are each H, and each X is benzyl (Bn), where the Hf phenol- oxadiazole complex can be represented by structure (VII):structure (VII).

[0019] One or more embodiments provide that R1is F, R6is a C4 alkyl, and R2- R5are each H, and each X is benzyl (Bn), where the Hf phenol-oxadiazole complex can be represented by structure (VIII):structure (VIII).

[0020] As used herein, all reference to the Periodic Table of the Elements and groups thereof is to the NEW NOTATION published in HAWLEYS CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced there with permission from IUPAC), unless reference is made to the Previous IUPAC form noted with Roman numerals (also appearing in the same), or unless otherwise noted.

[0021] As used herein, an “alkyl” includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen. Thus, for example, CH3 (“methyl”), i.e. C1 alkyl, and CH2CH3 (“ethyl”), i.e. C2 alkyl, are examples of alkyls.

[0022] As used herein, all percents refer to weight percent unless otherwise noted.

[0023] Embodiments provide that the Hf phenol-oxadiazole complexes discussed herein can be supported. Utilizing the support may be accomplished by any technique used in the art. The support may be functionalized. Spray-dried compositions can include a support, e.g., a spray dried support.

[0024] A “support”, which may also be referred to as a “carrier”, refers to any support material, including a porous support material, such as talc, inorganic oxides, and inorganic chlorides. Other support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

[0025] Support materials include inorganic oxides that include Group 2, 3, 4, 5, 13 or 14 metal oxides. The terms “support”, “solid support”, “support material”, and “solid support material” may be used interchangeably, and herein refer to a porous inorganic substance or organic substance. Some preferred supports include silica, fumed silica, alumina, silica-alumina, and mixtures thereof. Some other supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica- alumina, silica-titania and the like. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymeric beads. An example of a support is fumed silica available under the trade name CABOSIL TS- 610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that has been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.

[0026] Embodiments provide that the inorganic oxide support material is porous and has variable surface area, pore volume, and average particle size. In some embodiments, the surface area is from 50 to 1000 square meter per gram (m2 / g) and the average particle size is from 1 to 300 micrometers (pm), alternatively 20 to 300 pm. Alternatively, the pore volume is from 0.5 to 6.0 cubic centimeters per gram (cm2 / g) and the surface area is from 200 to 600 m2 / g. Alternatively, the pore volume is from 1 .1 to 1 .8 cm2 / g and the surface area is from 245 to 375 m2 / g. Alternatively, the pore volume is from 2.4 to 3.7 cm3 / g and the surface area is from 410 to 620 m2 / g. Alternatively, the pore volume is from 0.9 to 1 .4 cm2 / g and the surface area is from 390 to 590 m2 / g.Each of the above properties are measured using conventional techniques known in the art.

[0027] The support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 m2 / g. Such silicas are commercially available from several sources including theDavison Chemical Division of W.R. Grace and Company, e.g., Davison 952 and Davison 955 products, and PQ Corporation, e.g., ES70 product. The silica may be in the form of spherical particles, which may be obtained by a spray-drying process. Alternatively, MS3050 product is a silica from PQ Corporation that is not spray-dried. As procured, these silicas are not calcined, i.e., not dehydrated. Silica that is calcined prior to purchase may also be used as the support material.

[0028] In some embodiments the solid support is a hydrophobic fumed silica. The hydrophobic fumed silica is made by contacting an untreated fumed silica, having surfaces containing silicon-bonded hydroxyl groups (Si-OH groups), with a hydrophobing agent, described later. In some embodiments the hydrophobing agent is a silicon-based hydrophobing agent, containing on average per molecule one or more functional groups reactive with a Si-OH group, to give the hydrophobic fumed silica. The silicon-based hydrophobing agent may be selected from (CH3)2SiCl2, a polydimethylsiloxane, hexamethyldisilazane (HMDZ), and a (Ci -C-| Q)alkylSi((C-| -C-| Q)alkoxy)3 (e.g., an octyltrialkoxysilane such as octyltriethoxysilane, i.e., CH3(CH2)7Si(OCH2CH3)3). In some embodiments the silicon-based hydrophobing agent is dimethyldichlorosilane, i.e., (CH3)2SiCl2- In some embodiments the support material is a dimethyldichlorosilane- treated fumed silica, such as that sold as product TS-610 from Cabot Corporation.

[0029] The support material may be uncalcined or calcined. The calcined support material is made prior to being contacted with a precatalyst, activator, and / or hydrophobing agent, by heating the support material in air to give a calcined support material. The calcining comprises heating the support material at a peak temperature from 350 °C to 850 °C, alternatively from 400 °C to 800 °C, alternatively from 400 °C to 700 °C, alternatively from 500° to 650° C and for a time period from 2 to 24 hours, alternatively from 4 to 16 hours, alternatively from 8 to 12 hours, alternatively from 1 to 4 hours, thereby making the calcined support material. If the support material has not been heated in this way it can be referred to as an uncalcined support material.

[0030] As mentioned, the Hf phenol-oxadiazole complexes discussed herein can be utilized to make supported catalyst systems and / or compositions. In some embodiments the Hf phenol-oxadiazole complex and a support material are contacted together in an inert hydrocarbon liquid to give a suspension in the inert hydrocarbon liquid, then the suspension is contacted with an activator to give a suspension of thesupported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed, e.g., by spray drying, to give the supported catalyst system.

[0031] In some embodiments the Hf phenol-oxadiazole complex and an activator are contacted together in an inert hydrocarbon liquid to give a solution of a catalyst in the inert hydrocarbon liquid, then the solution is contacted with the support material to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.

[0032] In some embodiments the activator and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported activator in the inert hydrocarbon liquid, then the suspension is contacted with the Hf phenol-oxadiazole complex to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.

[0033] In some embodiments the Hf phenol-oxadiazole complex, the activator, and the support material are contacted together simultaneously in an inert hydrocarbon liquid to give a suspension of the supported catalyst, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.

[0034] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may include a step of decanting some of the inert hydrocarbon liquid from the suspension. In some embodiments the decanting method comprises pouring off excess inert hydrocarbon liquid from the suspension to give a concentrated suspension of the supported catalyst system.

[0035] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may comprise a step of drying the supported catalyst system. The drying step can include a spray-drying method.

[0036] The Hf phenol-oxadiazole complex discussed herein can be utilized to make spray-dried compositions. As used herein, “spray-dried composition” refers to a composition that includes a number of components that have undergone a spray-drying process. Various spray-drying process are known in the art and are suitable for forming the spray-dried compositions disclosed herein. One or more embodiments provide that the Hf phenol-oxadiazole complex, an activator, and the support are spray-dried to make the spray-dried composition. One or more embodiments provide that the spray-dried composition comprises a trim composition.

[0037] In one or more embodiments, the spray-drying process may comprise atomizing a composition including the Hf phenol-oxadiazole complex. A number of other known components may be utilized in the spray-drying process. An atomizer, such as an atomizing nozzle or a centrifugal high speed disc, for example, may be used to create a spray or dispersion of droplets of the composition. The droplets of the composition may then be rapidly dried by contact with an inert drying gas. The inert drying gas may be any gas that is non-reactive under the conditions employed during atomization, such as nitrogen, for example. The inert drying gas may meet the composition at the atomizer, which produces a droplet stream on a continuous basis. Dried particles of the composition may be trapped out of the process in a separator, such as a cyclone, for example, which can separate solids formed from a gaseous mixture of the drying gas, solvent, and other volatile components.

[0038] A spray-dried composition may have the form of a free-flowing powder, for instance. After the spray-drying process, the spray-dried composition and a number of known components, for instance, may be utilized to form a slurry. The spray-dried composition may be utilized with a diluent to form a slurry suitable for use in olefin polymerization, for example. In one or more embodiments, the slurry may be combined with one or more additional catalysts or other known components prior to delivery into a polymerization reactor.

[0039] In one or more embodiments, the spray-dried composition may be formed by contacting a spray dried activator particle, such as spray dried fumed silica (e.g., Cabosil) and methylaluminoxane(MAO), with a solution of the Hf phenol-oxadiazole complex. Such a solution of the Hf phenol-oxadiazole complex can be made in an inert hydrocarbon solvent, for instance, and is sometimes called a trim solution. Such a spray- dried composition comprised of contacting a trim solution of the Hf phenol-oxadiazole complex with a spray dried activator particle, such as spray-dried MAO, may be made in situ in a feed line heading into a slurry or gas phase polymerization reactor by contacting the trim solution with a slurry, typically in mineral oil, of the spray-dried activator particle.

[0040] As an example, various spray-drying conditions may be utilized for different applications. For instance, the spray-drying process may utilize a drying temperature from 115 to 185 °C. Various sizes of orifices of the atomizing nozzle employed during the spray-drying process may be utilized to obtain different particle sizes. Alternatively, for other types of atomizers such as discs, rotational speed, disc size, and number / size of holes may be adjusted to obtain different particle sizes. One ormore embodiments provide that a filler may be utilized in the spray-drying process. Different fillers and amounts thereof may be utilized for various applications.

[0041] The compositions discussed herein e.g., the spray-dried Hf phenoloxadiazole complex compositions, may be utilized to make polyolefins (polymers). For instance, the Hf phenol-oxadiazole complex may be activated, i.e. with an activator, to make a catalyst. One or more embodiments provide that the spray-dried compositions include an activator. As used herein, "activator" refers to any compound or combination of compounds, supported, or unsupported, which can activate a complex or a catalyst component, such as by creating a cationic species of the catalyst component, e.g., to provide the catalyst. The activator may also be referred to as a "co-catalyst". The activator can include a Lewis acid or a non-coordinating ionic activator or ionizing activator, or any other compound including Lewis bases, aluminum alkyls, and / or conventional-type co-catalysts. Activators include methylaluminoxane (MAO) and modified methylaluminoxane (MMAO), among others. One or more embodiments provide that the activator is methylalu inoxane. Activating conditions are well known in the art. Known activating conditions may be utilized.

[0042] The activator used may be any compound capable of reacting with the precatalyst of the structures discussed herein to provide an active olefin polymerization catalyst. The activator may be a Lewis acid, a non-coordinating ionic activator, or an ionizing activator, or a Lewis base.

[0043] A molar ratio of metal, e.g., aluminum, in the activator to Hf in the Hf phenol-oxadiazole complex may be 3500: 1 to 0.5: 1 , 1500 : 1 to 0.5: 1 , 750 : 1 to 0.5 : 1 , 300 : 1 to 0.5 : 1 , or 150: 1 to 1 : 1 . One or more embodiments provide that the molar ratio of metal in the activator to Hf in the Hf phenol-oxadiazole complex is at least 75:1 . One or more embodiments provide that the molar ratio of metal in the activator to Hf in the Hf phenol-oxadiazole complex is at least 100:1 . One or more embodiments provide that the molar ratio of metal in the activator to Hf in the Hf phenol-oxadiazole complex is at least 150:1 . One or more embodiments provide that the molar ratio of metal in the activator to Hf in the Hf phenol-oxadiazole complex is at least 300:1 . One or more embodiments provide that the molar ratio of metal in the activator to Hf in the Hf phenol- oxadiazole complex is at least 750:1 .

[0044] Suitable activators are commercially available. In some embodiments the aluminum based activator is an alkylaluminum or an alkylaluminoxane (alkylalumoxane). Any alkyl group may be utilized. In some embodiments, each alkyl of the alkylaluminumor alkylaluminoxane independently may be a (C-j -Cs)alkyl, alternatively a (C-j -Cyjalkyl, alternatively a (C-| -Cg)alkyl, alternatively a (C-| -C4)alkyl.

[0045] The alkylaluminum may be a trialkylaluminum, alkylaluminum halide, or alkylaluminum alkoxide (diethylaluminum ethoxide). The trialkylaluminum may be trimethylaluminum, triethylaluminum (“TEAI”), tripropylaluminum, or tris(2- methylpropyl)aluminum. The alkylaluminum halide may be diethylaluminum chloride. The alkylaluminum alkoxide may be diethylaluminum ethoxide.

[0046] Embodiments provide that the spray-dried composition includes from 1 to 12 wt% of the Hf phenol-oxadiazole complex, based on a total weight (100 wt%) of the Hf phenol-oxadiazole complex, the activator, and the support. All individual values and subranges from 1 to 12 wt% are included; for example, the spray-dried composition can include the Hf phenol-oxadiazole complex from a lower limit of 1 , 1 .5, or 1 .7 wt% to an upper limit of 12, 10, or 9 wt% of the Hf phenol-oxadiazole complex, based on the total weight of the Hf phenol-oxadiazole complex, the activator, and the support.

[0047] Embodiments provide that the spray-dried composition includes from 25 to 50 wt% of the activator, based on a total weight of the Hf phenol-oxadiazole complex, the activator, and the support. All individual values and subranges from 25 to 50 wt% are included; for example, the spray-dried composition can have from a lower limit of 25, 30, or 33 wt% to an upper limit of 50, 45, or 42 wt% of activator, based on the total weight of the Hf phenol-oxadiazole complex, the activator, and the support.

[0048] Embodiments provide that the spray-dried composition includes from 40 to 70 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex, the activator, and the support. All individual values and subranges from 40 to 70 wt% are included; for example, the spray-dried composition can have from a lower limit of 40 45, or 50 wt% to an upper limit of 70, 65, or 60 wt% of support, based on the total weight of the Hf phenol-oxadiazole complex, the activator, and the support.

[0049] The spray-dried compositions including the Hf phenol-oxadiazole complex and an olefin can be contacted under polymerization conditions to make a polymer, e.g., a polyolefin polymer. The catalyst system can include the Hf phenol-oxadiazole complex; an activator; and a support, which are discussed herein. Embodiments provide that the polymerization process is a gas-phase polymerization process. The polymerization process may utilize using known equipment and reaction conditions, e.g., known polymerization conditions. The polymerization process is not limited to any specific type of gas-phase polymerization system. The polyolefins can be utilized for a number ofarticles such as films, fibers, pipes, nonwoven and / or woven fabrics, extruded articles, and / or molded articles.

[0050] Embodiments provide that the polyolefins are made utilizing a gas-phase reactor system. One or more embodiments provide that a single gas-phase reactor, e.g., in contrast to a series of reactors, is utilized. In other words, polymerization reaction occurs in only one reactor. For instance, the polyolefins can be made utilizing a fluidized bed reactor. Gas-phase reactors are known and known components may be utilized for the fluidized bed reactor.

[0051] As used herein an “olefin,” which may be referred to as an “alkene,” refers to a linear, branched, or cyclic compound including carbon and hydrogen and having at least one double bond. As used herein, when a polyolefin, polymer, and / or copolymer is referred to as comprising, e.g., being made from, an olefin, the olefin present in such polyolefin, polymer, or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 75 wt% to 95 wt%, it is understood that the polymer unit in the copolymer is derived from ethylene in the polymerization reaction(s) and the derived units are present at 75 wt% to 95 wt%, based upon the total weight of the polymer. A higher a-olefin refers to an a-olefin having 3 or more carbon atoms.

[0052] Polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex discussed herein can made from olefin monomers such as ethylene, i.e., polyethylene, and 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, butene, pentene, 1 -hexene (which can be referred to more simply as hexene), and 1 -octene. Examples of polyolefins include ethylene-based polymers, having at least 50 wt % ethylene, including ethylene-1 -butene, ethylene-1 - hexene, and ethylene- 1 -octene copolymers, among others. One or more embodiments provide that the polymer can include from 50 to 99.9 wt % of units derived from ethylene based on a total weight of the polymer. All individual values and subranges from 50 to 99.9 wt % are included; for example, the polymer can include from a lower limit of 50, 60, 70, 80, or 90 wt % of units derived from ethylene to an upper limit of 99.9, 99.7, 99.4, 99, 96, 93, 90, or 85 wt % of units derived from ethylene based on the total weight of the polymer. The polymer can include from 0.1 to 50 wt % of units derived from comonomer based on the total weight of the polymer. One or more embodiments provide that ethylene is utilized as a monomer and 1 -hexene is utilized as a comonomer to make acopolymer. One or more embodiments provide that ethylene is utilized to make a homopolymer.

[0053] As mentioned, the polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can be made in a fluidized bed reactor. The fluidized bed reactor can have a reaction temperature from 10 to 130 °C. All individual values and subranges from 10 to 130 °C are included; for example, the fluidized bed reactor can have a reaction temperature from a lower limit of 10, 20, 30, 40, 50, or 55 °C to an upper limit of 130, 120, 1 10, 100, 90, 80, 70, or 60 °C.

[0054] The fluidized bed reactor can have an ethylene partial pressure from 30 to 300 pounds per square inch (psi). All individual values and subranges from 30 to 300 are included; for example, the fluidized bed reactor can have an ethylene partial pressure from a lower limit of 30, 45, 60, 75, 85, 90, or 95 psi to an upper limit of 300, 240, 220, 200, 150, or 125 psi.

[0055] One or more embodiments provide that ethylene is utilized as a monomer and hexene is utilized as a comonomer. The fluidized bed reactor can have a comonomer to ethylene mole ratio, e.g., C5 / C2, from 0.0001 to 0.100. All individual values and subranges from 0.0001 to 0.100 are included; for example, the fluidized bed reactor can have a comonomer to ethylene mole ratio from a lower limit of 0.0001 , 0.0005, 0.0007, 0.001 , 0.0015, or 0.002 to an upper limit of 0.100, 0.080, or 0.050.

[0056] When hydrogen is utilized for a polymerization process, the fluidized bed reactor can have a hydrogen to ethylene mole ratio (H2 / C2) from 0.00001 to 0.90000, for instance. All individual values and subranges from 0.00001 to 0.90000 are included; for example, the fluidized bed reactor can have a H2 / C2 from a lower limit of 0.00001 , 0.00005, or 0.00008 to an upper limit of 0.90000, 0.500000, 0.10000, 0.01500, 0.00700, or 0.00500. One or more embodiments provide that hydrogen is not utilized.

[0057] The polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can have a density from 0.8700 to 0.9700 g / cm3. All individual values and subranges from 0.8700 to 0.9700 g / cm3are included; for example, the polyolefins can have a density from a lower limit of 0.8700, 0.9000, 0.9100, or 0.9150 g / cm3to an upper limit of 0.9700, 0.9650, 0.9500, 0.9550, or 0.9300 g / cm3.Density can be determined by according to ASTM D792.

[0058] The polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can have a number average molecular weight (Mn) from10,000 to 350,000 g / mol. All individual values and subranges from 10,000 to 350,000 g / mol are included; for example, the polyolefins can have an Mn from a lower limit of 10,000, 20,000, or 35,000 g / mol to an upper limit of 350,000, 250,000, 200,000, or 150,000 g / mol. Mw can be determined by gel permeation chromatography (GPC), as is known in the art. GPC is discussed herein.

[0059] The polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can have a weight average molecular weight (Mw) from 20,000 to 1 ,000,000 g / mol. All individual values and subranges from 20,000 to 1 ,000,000 g / mol are included; for example, the polyolefins can have an Mwfrom a lower limit of 20,000, 80,000, 100,000, or 175,000 g / mol to an upper limit of 1 ,000,000, 800,000, 600,000, 500,000, or 475,000 g / mol. Mw can be determined by gel permeation chromatography (GPC), as is known in the art. GPC is discussed herein.

[0060] The polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can have a z average molecular weight (Mz) from 100,000 to 10,000,000 g / mol. All individual values and subranges from 100,000 to 10,000,000 g / mol are included; for example, the polyolefins can have an Mz from a lower limit of 100,000, 200,000, 370,000, or 475,000 g / mol to an upper limit of 10,000,000, 800,000, or 600,000 g / mol. Mz can be determined by gel permeation chromatography (GPC), as is known in the art. GPC is discussed herein.

[0061] The polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can have a melt temperature (Tm) from 100 to 160 °C. All individual values and subranges from 100 to 160 °C are included; for example, the polyolefins can have an Tm from a lower limit of 100, 103, or 105 °C to an upper limit of 160, 150, 145, or 140 °C. Melt temperature can be determined by Differential Scanning Calorimetry according to ASTM D 3418-08.

[0062] As mentioned, advantageously, the compositions discussed herein can be utilized to make polyolefins having long chain branching via gas phase polymerizations. Long chain branching is generally not observed in products made via gas phase. Embodiments provide that the polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can have long chain branching as indicated by as indicated by13C NMR and / or Mark-Houwink plotting.

[0063] As mentioned, advantageously, the polyolefins made with the spray-dried compositions including the Hf phenol-oxadiazole complex can have an advantageous polydispersity index (Mw / Mn) from 1.5 to 6.0. Polydispersity index can be determinedaccording to GPC, as discussed herein. All individual values and subranges from 1 .5 to 6.0 are included; for example, the polyolefins can have a polydispersity index from a lower limit of 1 .5, 2.0 or 2.9 to an upper limit of 6.0, 5.5, or 4.9. This decreased and / or narrowed, polydispersity index, as compared to other compositions made with a number of other catalysts, can provide more catalyst and / or polyethylene resin design degrees of freedom along and / or enhanced polyethylene product performance.EXAMPLES

[0064] Example 1 , a spray-dried composition including a Hf phenol-oxadiazole complex, was made as follows. The Hf phenol-oxadiazole complexes of structures (II)- (VIII) were obtained from The Dow Chemical Company.

[0065] Silica (fumed silica; CAB-O-SIL TS-610; Cabot corporation; 0.66 g).) and toluene (18.75 g) were added to a container, followed by addition of a 10 % solution (5.5 g) by weight of MAO in toluene. A Hf phenol-oxadiazole complex of structure (II), where Ar is 2,6-ChPh, (0.092 g).structure (II)

[0066] was added to the contents of the container; then, the contents of the container were stirred at approximately 20 °C for approximately 45 minutes. Then, the contents of the container were introduced into an atomizing device, to produce droplets that were then contacted with a hot nitrogen gas stream to evaporate the liquid and form a powder. The powder was separated from the gas mixture in a cyclone separator and discharged to provide Example 1 . The spray drier temperature was set at 160 °C and the outlet temperature at 70-80 °C.

[0067] Example 1 included 7.5 wt% of the Hf phenol-oxadiazole complex of structure (II), 38.9 wt% of the activator, and 53.6 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0068] Example 2 was made as Example 1 , with the change that a Hf phenoloxadiazole complex of structure (III), where Ar is 2,6-Cl2Ph, (0.090 g) was utilized, rather than the Hf phenol-oxadiazole complex of structure (II):structure (III).

[0069] Example 2 included 7.3 wt% of the Hf phenol-oxadiazole complex of structure (III), 38.9 wt% of the activator, and 53.7 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0070] Example 3 was made as Example 1 , with the change that a Hf phenol- oxadiazole complex of structure (IV), where Ar is 2,6-Cl2Ph, (0.09 g) was utilized, rather than the Hf phenol-oxadiazole complex of structure (II):structure (IV).

[0071] Example 3 included 7.3 wt% of the Hf phenol-oxadiazole complex of structure (IV), 38.9 wt% of the activator, and 53.7 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0072] Example 4 was made as Example 1 , with the change that a Hf phenol- oxadiazole complex of structure (V), where Ar is 2,6-Cl2Ph, (0.087 g) was utilized, rather than the Hf phenol-oxadiazole complex of structure (II):structure (V).

[0073] Example 4 included 7.1 wt% of the Hf phenol-oxadiazole complex of structure (V), 39.0 wt% of the activator, and 53.9 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0074] Example 5 was made as Example 1 , with the change that a Hf phenol- oxadiazole complex of structure (VI), where Ar is 2,6-Cl2Ph, (0.089 g) was utilized, rather than the Hf phenol-oxadiazole complex of structure (II):structure (VI).

[0075] Example 5 included 7.3 wt% of the Hf phenol-oxadiazole complex of structure (VI), 39.0 wt% of the activator, and 53.8 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0076] Example 6 was made as Example 1 , with the change that a Hf phenol- oxadiazole complex of structure (VII), where Ar is 2,6-ChPh, (0.094 g) was utilized, rather than the Hf phenol-oxadiazole complex of structure (II):structure (VII).

[0077] Example 6 included 7.6 wt% of the Hf phenol-oxadiazole complex of structure (VII), 38.8 wt% of the activator, and 53.5 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0078] Example 7 was made as Example 1 , with the change that a Hf phenol- oxadiazole complex of structure (VIII), where Ar is 2,6-Cl2Ph, (0.087 g) was utilized, rather than the Hf phenol-oxadiazole complex of structure (II):structure (VIII).

[0079] Example 7 included 7.1 wt% of the Hf phenol-oxadiazole complex of structure (VIII), 39.0 wt% of the activator, and 53.9 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0080] Gas-phase batch reactor Polymerizations 1-9 were performed respectively utilizing Examples 1 -7 as follows. Polymerizations 1 -7 made respective C2 homopolymers.

[0081] For respective polymerizations, a lab-scale gas phase polymerization reactor (2-liter, stainless steel autoclave equipped with a variable speed mechanical agitator) was charged with dried NaCI (400 g) and heated to 100 °C under a stream of nitrogen for one hour. Then the reactor was purged with nitrogen, silica supported methylaluminoxane (SMAO) was added as a scavenger to the reactor. After adding SMAO, the reactor was sealed and components were stirred. Then hydrogen was charged and the reactor was pressurized with ethylene (total pressure = 220 psi). Once the system reached a steady state, the catalyst system (respectively Examples 1 -7) was charged into the reactor to start polymerization. The reactor temperature was brought to the predetermined temperature and maintained at this temperature throughout the polymerization. The polymerization was carried out for 60 minutes. At the end of the 60 minutes, the reactor was cooled down, vented and opened. The resulting product was washed with water, isopropanol and dried. Polymerization Activity (grams polymer / gram catalyst-hour) was determined as a ratio of an amount of polymer produced to an amount of catalyst added to the reactor. Polymerization conditions, reported as anaverage from four polymerization runs, and a number of properties are reported in the following Tables.Table 1Table 2Table 3

[0082] The data of Table 3 illustrate that utilizing Examples 1 -7 provides polymers having a Mw / Mn from 1 .5 to 6.0.

[0083] Gas-phase batch reactor Polymerizations 8-21 were performed respectively utilizing Examples 1 -7 as follows. Polymerizations 8-21 made respective C2 / C6 copolymers.

[0084] For respective polymerizations, a lab-scale gas phase polymerization reactor (2-liter, stainless steel autoclave equipped with a variable speed mechanical agitator) was charged with dried NaCI (400 g) and heated to 100 °C under a stream of nitrogen for one hour. Then the reactor was purged with nitrogen, silica supported methylaluminoxane (SMAO) was added as a scavenger to the reactor. After adding SMAO, the reactor was sealed and components were stirred. Then hydrogen was charged and the reactor was pressurized with ethylene (total pressure = 220 psi) and hexene was pumped in at a predetermined C6 / C2 ratio simultaneously. Once the system reached a steady state, the catalyst system (respectively Examples 1-7) was charged into the reactor to start polymerization. The reactor temperature was brought to the predetermined temperature and maintained at this temperature throughout the polymerization. The polymerization was carried out for 60 minutes. At the end of the 60minutes, the reactor was cooled down, vented and opened. The resulting product was washed with water, isopropanol and dried. Polymerization Activity (grams polymer / gram catalyst-hour) was determined as a ratio of an amount of polymer produced to an amount of catalyst added to the reactor. Polymerization conditions, reported as an average from four polymerization runs, and a number of properties are reported in the following Tables.Table 4Table 5Table 6

[0085] The data of Table 6 illustrate that utilizing Examples 1 -7 provides polymers having a Mw / Mn from 1 .5 to 6.0.

[0086] Examples 8-A and 8-B were made with the Hf phenol-oxadiazole complex of structure (IX) as follows.Structure (IX).

[0087] An oil-jacketed, 10 gallon, continuously stirred tank reactor (CSTR), was used for the preparation of all catalyst slurry feeds in this experiment. Catalyst slurries were mixed at 23 °C during preparation with 6 psig of nitrogen. The catalyst slurries were agitated and recirculated using a Pulsafeeder diaphragm metering pump, which isthe same type of pump used to feed the catalyst slurry to the Spray Dryer atomizer. The agitation rate was maintained at 400 rpm. Between the CSTR and the diaphragm pump, was a set of filters containing a 20 mesh tapered screen element inside. Electrical heat tracing was kept energized on the process lines, filters, and diaphragm pump to provide that the slurries did not thicken from ambient temperature loss.

[0088] Toluene (Example 8-A: 15.6 lbs; Example 8-B: 13.7 lbs) was added to the CSTR and the agitator (400 rpm) was activated to provide slurry mixing. Next, a 10% solution of MAO mixed in toluene was added (Example 8-A: 12.8 lbs; Example 8-B: 12.7 lbs). The utilized liquids were added to the CSTR prior to other components to provide a heat sink for any exothermic reactions from catalyst material to be added, as well as to provide desired mixing of later added solid materials. Then, CABOSIL TS-610 fumed silica (Example 8-A: 1.47 lbs; Example 8-B: 1.53 lbs) was added, followed by the phenoloxadiazole complex of structure (XI) (Example 8-A: 24.6 g; Example 8-B: 32.7 g), which was added via Swagelok stainless steel cylinders connected directly to the charge port on the CSTR. A toluene flush was used after each cylinder addition to CSTR to provide delivery of any residual material into the CSTR. After all of the components were introduced to CSTR, the components were mixed for 1 hour at 23 °C to provide a catalyst slurry utilized for spray drying.

[0089] After the catalyst slurry was prepared, a three-way valve was actuated to cease recirculation to the CSTR and instead send the catalyst slurry to a Spray Drying atomizer. This rotary atomizer was equipped with a 4-hole wheel assembly (GEA engineering, model FX-1), and was spun at setpoint (17,500 rpm to 22,500 rpm) before the catalyst slurry was injected. In order to reach the desired exit temperature and provide that the holes were clean, fresh solvent was purged through the atomizer holes until the specified exit temperature was reached for every run. The droplets of slurry were rapidly dried at the exit of the atomizer holes due to contact with a heated cycle gas also coming in the spray drying chamber. The entering cycle gas temperature was approximately 130 °C, and the resulting exit temperature of this chamber was approximately 83 °C.

[0090] Then, cycle gas was utilized to transfer dried solid particles into a solids separating cyclone. This was a tangential entry port reverse flow cyclone, model CHE- 300 from GEA Engineering. Solids separated from the cyclone were then dropped into a container at the bottom of the cyclone. The first approximately 15 weight percent % of the dried material was discarded. The separated cycle gas from the cyclone then wentinto a recirculation blower and a solvent condensing tower. The tower was cooled with a constantly recirculated refrigerated oil system to approximately -15 °C. Collected solvents were discarded. Cycle gas exiting the condensing tower at approximately 0 °C was then heated to maintain the exit temperature after the spray dryer chamber. When each batch was complete, the atomizer holes were flushed again with fresh solvent. The collected supported catalyst was sampled for analysis, and then transferred to a container under an inert environment and stored with positive nitrogen pressure in refrigerated storage (-10°C).

[0091] Example 8-A included 1 .9 wt% of theHf phenol-oxadiazole complex of structure (XI), 41 .0 wt% of the activator, and 57.1 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0092] Example 8-B included 2.5 wt% of the Hf phenol-oxadiazole complex of structure (XI), 40.8 wt% of the activator, and 56.8 wt% of the support, based on a total weight of the Hf phenol-oxadiazole complex of structure, the activator, and the support.

[0093] Particle size of Examples 8-A and 8-B was measured using a Malvern Mastersizer 3000 (Model MAZ3000) with a Small Volume Sample Dispersion Unit (Model MAZ3150). The samples were dispersed in heptanes (Fisher Scientific) to perform the measurement. The results are reported in the following Table.

[0094] Hf and Al loading of Examples 8-A and 8-B was determined by X-ray Fluorescence (XRF). Sample beads for XRF analysis were prepared using potassium iodide and a LeNeo Fusion Bead Maker. The XRF analysis was performed using a PANalytical Axios X-Ray Spectrometer. The results are reported in the following Table.Table 7

[0095] Gas-phase batch reactor Polymerizations 22-27 (P. 22-27) were performed respectively utilizing Examples 8-A, 8-B (Ex. 8A-8B) as follows. Polymerizations 22-27 made respective C2 / C6 copolymers.

[0096] A gas phase fluidized bed reactor (14 inch OD with approximately a 7 foot tall straight side operating at 350 psig total pressure) was utilized. The recycle loop circulated approximately 12,000 Ibs / hr of gas. The recirculation loop included a centrifugal compressor and cycle gas cooler. A slip stream of recycle gas was taken from the compressor discharge and was then split, where one stream was used to purge the discharge valve and one stream is used to disrupt the catalyst spray zone in the bed, acting as a particle agglomeration lever. The cooled gas in the recirculation loop exited the cycle gas cooler was routed to the bottom head of the reactor where it passed through a distributor plate and then entered the bed. The bed weight was controlled to a preset value by automatic discharge cycles to a product discharge tank where monomers were purged from the resin before the resin was dumped to a product drum.

[0097] Slurry catalyst was fed via a syringe feeder. Nitrogen was used to disperse the catalyst mixture in the reactor via a 1 / 8” injection nozzle. A %” shroud including nitrogen and isopentane sweep surrounded the injection nozzle. The shroud reduced catalyst build up on the outside of the injection nozzle. An onstream cycle gas analyzer monitored gas concentration and an Advanced Process Control (APC) system was used to control the gas feed stream flow rates to maintain the desired compositions. Density was controlled by adjusting the hexene to ethylene gas concentration and MFR was controlled by adjusting the hydrogen to ethylene gas concentration. The results are reported in the following Table.Table 8

[0098] The data of Table 8 illustrate that utilizing Examples 8-A and 8-B provides polymers having long chain branching via gas phase polymerizations, as indicated by 13C NMR and Mark-Houwink plotting.

[0099] The data of Table 6 illustrate that utilizing Examples 1 -7 provides polymers having a Mw / Mn from 1 .5 to 6.0.

[0100] Long chain branching as indicated by13C NMR was determined as follows. Approximately 100 mg of the polymer sample was added to 2.7 mL of 1- choloronaphthelene / PDCB-d4 (9:1 , w / w) with 0.025 M Cr(acac)3 and 100 ppm 1-168 in a 10 mm NMR tube. The sample tube was heated to 130 to 135 °C to facilitate polymer melting and subsequent dissolution. The heated sample was homogenized using a vortexer until consistent flow was achieved. The NMR spectra were collected on a Broker 600 MHz AVANCE III HD system equipped with a 10 mm high-temperature helium cooled cryoprobe at 120 °C. NMR spectra were processed with MNova.

[0101] Long chain branching as indicated by a Mark-Houwink Plot was determined.

[0102] Melt index (I2) was determined according to ASTM D 3418-08 (190 °C, 2.16 kg). Melt index (I5) was determined according to ASTM D 3418-08 (190 °C, 5 kg). Melt index (I21 )wasdetermined according to ASTM D 3418-08 (190 °C, 21 .6 k).

[0103] Density was determined by according to ASTM D792.

[0104] Melt temperature (Tm) was determined via Differential Scanning Calorimetry according to ASTM D 3418-08. In general, a scan rate of 10° C / min on a sample (10 mg) was used, and the second heating cycle was used to determine Tm.

[0105] Mw, Mn, and Mz were determined by GPC.

[0106] GPC was determined as follows.

[0107] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5). The autosampler oven compartment was set at 165eC and the column compartment was set at 155eC. The columns used were 4 TOSOH TSK GMHHR-H (30) HT 30-micron sized, mixed pore size columns. The chromatographic solvent used was 1 ,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters and the flow rate was 1 .0 milliliters / minute.

[0108] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 g / mol and were arranged in 6 cocktail mixtures with at least a decade of separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1 ,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1 ,000,000. Thepolystyrene standards were pre-dissolved at 80eC with gentle agitation for 30 minutes then cooled and the room temperature solution is transferred cooled into the autosampler dissolution oven at 160eC for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).:

[0110] where M is the molecular weight, A has a value of 0.3992 and B is equal to 1.0.

[0111] A third order polynomial was used to fit the respective polyethyleneequivalent calibration points.

[0112] The total plate count of the GPC column set was performed with decane which was introduced into blank sample via a micropump controlled with the PolymerChar GPC-IR system. The plate count for the chromatographic system should be greater than 12,000 for the 4 TOSOH TSK GMHHR-H (30) HT 30-micron sized, mixed pore size columns.

[0113] Samples were prepared in a semi-automatic manner with the PolymerChar Instrument Control Software, wherein the samples were weight-targeted at 2 mg / ml, and the solvent (contained 200ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 3 hours at 165eC under low speed shaking.

[0114] The calculations of Mn(GPC), MW(GPC), and MZ(GPC) were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC- IR chromatograph according to Equations 2-4, using PolymerChar GPCONE software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation 1 .

[0118] To monitor the deviations over time, a flowrate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flowrate marker (PM) was used to linearly correct the pump flowrate (Flowrate(nominai)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM sample)) to that of the decane peak within the narrow standards calibration (RV(FM calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 5. Processing of the flow marker peak was done via the PolymerChar GPCONE Software. Acceptable flowrate correction is such that the effective flowrate should be within + / -0.5% of the nominal flowrate.

[0119] Flowrate(effective) = Flowrate(nominal) * (RV(FM Calibrated) I RV(FMSample)) (EQ5).

[0120] The comonomer content (C6 wt%), e.g., 1 -hexene, incorporated in the polymers was determined by rapid FT-IR spectroscopy on the dissolved polymer in a GPC measurement. Comonomer content was determined with respect to polymer molecular weight by use of an infrared detector (an IR5 detector) in a gel permeation chromatography measurement, as described in Analytical Chemistry 2014, 86(17), 8649-8656. “Toward Absolute Chemical Composition Distribution Measurement of Polyolefins by High-Temperature Liquid Chromatography Hyphenated with Infrared Absorbance and Light Scattering Detectors” by Dean Lee, Colin Li Pi Shan, David M.Meunier, John W. Lyons, Rongjuan Cong, and A. Willem deGroot. Analytical Chemistry 2014 86 (17), 8649-8656.

Claims

What is claimed is:1 . A spray-dried composition comprising: a Hf phenol-oxadiazole complex represented by structure (I):structure (I) wherein each Ar is 2,6-Cl2Ph, R1-R6 are each independently H, a C1 -C20 alkyl, fluorine (F), or trifluoromethyl (CF3), and each X is a leaving group; an activator; and a support.

2. The spray-dried composition of claim 1 , wherein the Hf phenol-oxadiazole complex is 1 to 12 wt%, the activator is 25 to 50 wt%, and the support is 40 to 70 wt%, based upon a total weight of the phenol-oxadiazole complex, the activator, and the support.

3. The spray-dried composition of any one of claims 1 -2, wherein the activator comprises methylaluminoxane.

4. The spray-dried composition of any one of claims 1 -3, wherein the support comprises silica.

5. The spray-dried composition of any one of claims 1 -4, wherein each X independently selected from fluoride, chloride, bromide, methyl, ethyl, phenyl, benzyl, phenyloxy, benzloxy, 2-phenyl-2-propoxy, 1-phenyl- 2-propoxy, 1 -phenyl-2-butoxy, and 2-phenyl-2-butoxy.

6. A method for providing polymers having long chain branching via a gas phase polymerization, the method comprising: contacting the spray-dried composition of any one of claims 1-5 and an olefin under polymerization conditions within a gas-phase reactor to make the polymers.

7. The method of claim 6, wherein the olefin comprises ethylene.

8. The method of claim 6, wherein the olefin comprises hexene.

9. The method of claim 6, wherein the gas-phase reactor is a fluidized bed reactor.

10. The method of claim 9. wherein the fluidized bed reactor has a reaction temperature from 10 to 130 °C and an ethylene partial pressure from 30 to 300 pounds per square inch.

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