Process for preparing catalyst precursor material

Abstract

A process for preparing a catalyst precursor material from a dihalo-substituted metalloid is provided. The process comprises mixing in a first reaction zone a first solution consisting of a haloalkane, at least one solvent, and a first component selected from a dihalo-substituted Group 14 metal or organolithium reagent. The first solution is continuously added to a second reaction zone, and a second solution is continuously added to the second reaction zone. The second solution comprises at least one solvent and a second component of the dihalo-substituted Group 14 metal or the organolithium reagent, the second component being different from the first component. The first solution and the second solution are mixed in the second reaction zone.

Description

[0001] This invention application is a divisional application based on a patent application with an application date of March 27, 2020, application number 202080029443.7 (international application number PCT / US2020 / 025239), and invention name “Method for preparing catalyst precursor materials”. Technical Field

[0002] The present invention relates generally to methods for preparing catalyst precursor materials from dihalide-substituted metalloids. Specifically, the present invention relates to methods for preparing catalyst precursor materials from dihalide-substituted Group 14 metalloids, halogenated alkanes, organolithium reagents and solvents in a continuous addition reaction. Background Art

[0003] Linear low-density ethylene-based polymers are designed and increasingly used to meet the growing demand for packaging, hygiene and medical products. Dihalogen-substituted metalloids can be used to form reaction catalysts for producing linear low-density ethylene-based polymer resins. However, the solutions used to produce these dihalogen-substituted metalloids are also prone to dissociation even under mild conditions, which makes the production of the dihalogen-substituted metalloids difficult and costly.

[0004] Current methods for preparing these catalyst precursor materials from dihalo-substituted metalloids require batch reactions, which are thermally unstable and can result in batch-to-batch purity variations. Therefore, alternative methods for producing these catalyst precursor materials are needed. For example, methods are needed that can increase yields and easily and consistently control the temperature of the reactants that form dihalo-substituted metalloids. Summary of the invention

[0005] According to one embodiment, a method includes: mixing a first solution in a first reaction zone, the first solution comprising a halogenated alkane, at least one solvent and a first component selected from a dihalide-substituted Group 14 metal or an organic lithium reagent; continuously adding the first solution to a second reaction zone; continuously adding a second solution to the second reaction zone, the second solution comprising at least one solvent and a second component selected from the dihalide-substituted Group 14 metal or the organic lithium reagent, wherein the second component is different from the first component; and mixing the first solution and the second solution in the second reaction zone.

[0006] According to other embodiments, a method includes: reacting an organolithium reagent, a haloalkane, and at least one solvent in a first reaction zone to form a first solution; continuously adding the first solution and a second solution to a second reaction zone, wherein the second solution includes a dihalo-substituted Group 14 metal and at least one solvent; and mixing the first solution and the second solution in the second reaction zone.

[0007] Additional features and advantages will be set forth in the following detailed description, and in part will become apparent to those skilled in the art from the detailed description or may be recognized by practicing the embodiments described herein, including the following detailed description, claims, and drawings.

[0008] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments and are incorporated into and constitute a part of this specification. The accompanying drawings illustrate the various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 schematically depicts a system for preparing a catalyst precursor material according to one or more embodiments disclosed and described herein;

[0010] Figure 2 schematically depicts an alternative system for preparing catalyst precursor material according to one or more embodiments disclosed and described herein; and

[0011] Figure 3 Depicted is a gas chromatography (GC) spectrum of a catalyst precursor material produced according to one or more embodiments disclosed and described herein. DETAILED DESCRIPTION

[0012] Reference will now be made in detail to an embodiment of a method for preparing a catalyst precursor material from a dihalide-substituted metalloid.Where possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

[0013] As used herein, the term "metalloid" refers to a chemical element whose properties are intermediate between those of metals and non-metals, or a mixture of those of metals and non-metals.

[0014] As used herein, the term "Group 14 metalloid" refers to a metalloid that is a member of Group 14 of the IUPAC periodic table. Examples of Group 14 metalloids include, but are not limited to, silicon and germanium.

[0015] As used herein, the term "dihalo-substituted Group 14 metalloid" refers to a Group 14 metalloid comprising (a) two halo substituents and (b) two additional substituents. The two halo substituents may include, but are not limited to, fluorine, bromine, chlorine, and iodine. The two halo substituents may be the same as or different from each other. The two additional substituents may be the same as or different from each other. In an embodiment, the additional substituent may include, but are not limited to, isopropyl, tert-butyl, hexyl, or a combination thereof.

[0016] As used herein, the term "haloalkane" refers to any alkane containing (a) 1 to 3 carbon atoms and (b) at least one halogenated substituent. The at least one halogenated substituent may include, but is not limited to, fluorine, bromine, chlorine, and iodine. In an embodiment, the halogenated alkane may include dihalomethane.

[0017] As used herein, the term "organolithium reagent" refers to any organometallic compound containing at least one carbon-lithium bond.

[0018] As used herein, the term "solvent" includes any substance capable of dissolving one or more of a dihalo-substituted Group 14 metal, an organolithium reagent, or a halogenated alkane. Suitable solvents may include, but are not limited to, any ether solvent, an alkyl solvent, or an aromatic solvent. The solvent may be present in any of the systems described herein, alone or in any combination.

[0019] Examples of suitable ether solvents may include, but are not limited to, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, and 1,2-dimethoxyethane.

[0020] Examples of suitable alkyl solvents can include, but are not limited to, any alkane containing from 1 carbon atom to 40 carbon atoms. In an embodiment, the alkyl solvent contains from 5 carbon atoms to 7 carbon atoms.

[0021] Examples of suitable aromatic solvents may include any suitable alkylbenzene compounds. Specific examples of suitable aromatic solvents include but are not limited to benzene, C2 benzene, C3 benzene or C4 benzene.

[0022] In an embodiment, a method for preparing a catalyst precursor material comprises: continuously adding a first solution comprising an organic lithium reagent, a halogenated alkane and at least one solvent to a first reaction zone; mixing the first solution in the first reaction zone; continuously adding the first solution and a second solution comprising a dihalide-substituted Group 14 metal and at least one solvent to a second reaction zone; and mixing the first solution and the second solution in the second reaction zone.

[0023] In another embodiment, a method for preparing a catalyst precursor material comprises: mixing a first solution in a first reaction zone, wherein the first solution includes a halogenated alkane, at least one solvent and a first component selected from a dihalide-substituted Group 14 metal or an organic lithium reagent; continuously adding the first solution to a second reaction zone; continuously adding a second solution to the second reaction zone, wherein the second solution includes at least one solvent and a second component selected from the dihalide-substituted Group 14 metal or the organic lithium reagent, wherein the second component is different from the first component; and mixing the first solution and the second solution in the second reaction zone.

[0024] Conventional methods for forming catalyst precursor materials include batch production methods performed in an ad hoc manner. Conventional methods include preparing a feed solution in a container cooled to at least -70°C in an acetone-dry ice bath, the feed solution comprising a dihalo-substituted Group 14 metal and a haloalkane in a solvent. The organolithium reagent is added to the container over a span of several hours, such as 6 hours, ensuring that the organolithium reagent is directed to the container wall to cool it before it is mixed with the other reactants. However, such batch production methods often result in errors, which may be caused by unexpected or uncontrolled temperature changes. These errors can cause the purity of the catalyst precursor material to be negatively affected.

[0025] In contrast, Figure 1-3 The system of the embodiment shown in is a continuous synthesis system in which reactants are continuously fed into one or more reaction zones. Figure 1-3 The embodiments depicted in provide a suitable system for preparing catalyst precursor materials.

[0026] Reference now Figure 1 , describes a system and method for producing a catalyst precursor material by feeding a continuous stream into a reaction zone. Figure 1 In the embodiment of the catalyst precursor material production system 100 shown, the contents of the first reagent feed tank 110 are introduced into the precooler 120 via the first reagent feed stream 112, which couples the first reagent feed tank 110 fluid to the precooler 120. The first reagent feed tank 110 can include any suitable storage device, such as a cooling container, optionally with the ability to mix its contents. It should be further understood that the first reagent feed tank 110 and the precooler 120 can be a single, combined physical unit ( Figure 1 ) or separate physical units fluidly coupled to each other.

[0027] A heat exchanger may optionally be added anywhere along the first reagent feed stream 112 to further cool the contents of the first reagent feed tank 110 before introducing the contents of the first reagent feed tank 110 into the pre-cooler 120. According to an embodiment, the contents of the first reagent feed tank 110 may comprise a mixture of a dihalogen-substituted Group 14 metal and a haloalkane, optionally in a solvent. In an embodiment, the solvent is an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

[0028] In an embodiment, the dihalogen-substituted Group 14 metal initially present in the first reagent feed tank 110 in the system may include, but is not limited to, dichlorodiisopropylsilane, di-tert-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-tert-butyldichlorogermane, dichlorodiphenylgermane, or a combination thereof. In certain embodiments, the dihalogen-substituted Group 14 metal present in the first reagent feed tank 110 is dichlorodiisopropylsilane.

[0029] In an embodiment, the halogenated alkane is also initially present in the first reagent feed tank 110 in the system, or may be added to the pre-cooler 120 in the system ( Figure 1 The halogenated alkane may be any suitable halogenated alkane, such as dihalomethane. Examples of suitable dihalomethanes include, but are not limited to, dibromomethane, dichloromethane, difluoromethane, diiodomethane, bromochloromethane, bromofluoromethane, bromoiodomethane, chlorofluoromethane, chloroiodomethane, fluoroiodomethane, or a combination thereof. In certain embodiments, the halogenated alkane initially present in the first reagent feed tank 110 is bromochloromethane.

[0030] Once the contents of precooler 120 (which, depending on the embodiment, may include equipment for mixing its components) reach a desired capacity, the contents of precooler 120 are continuously added to reaction zone 130 via feed stream 114 , which fluidly couples precooler 120 to reaction zone 130 .

[0031] It should be understood that the concentrations of the various components in the first reagent feed tank 110 can be modified by adding solvent to the first reagent feed stream 112 at any point before the feed stream 114 is added to the reaction zone 130, such as at the first reagent feed tank 110, to the precooler 120, or to the feed stream 114. Without being bound by theory, it is believed that if the concentration of the dihalo-substituted Group 14 metal and / or the haloalkane is too high or too low, it can negatively impact the dilution of the components, control of the reaction rate, mixing control, and system temperature maintenance.

[0032] At the same time, the contents of the second reagent feed tank 140 are fed by the second reagent feed stream 116 through the heat exchanger 150, which couples the second reagent feed tank 140 fluid to the heat exchanger 150. The second reagent feed tank 140 can include any suitable storage device, such as a cooling container, optionally with the ability to mix any of its contents. It should be further understood that the second reagent feed tank 140 and the heat exchanger 150 can be a single, combined physical unit ( Figure 1 ) or separate physical units.

[0033] Prior to continuous addition to reaction zone 130 , the contents of feed stream 114 and feed stream 118 are cooled to a temperature of 0° C. to −90° C., such as in precooler 120 and heat exchanger 150 . In an embodiment, feed stream 114 and feed stream 118 are independently cooled to a temperature of -5°C to -90°C, such as -10°C to -90°C, -15°C to -90°C, -20°C to -90°C, -25°C to -90°C, -30°C to -90°C, -35°C to -90°C, -40°C to -90°C, -45°C to -90°C, -50°C to -90°C, -55°C to -90°C, -60°C to -90°C, -65°C to -90°C, -70°C to -90°C, -75°C to -90°C, -80°C to -90°C, or -85°C to -90°C before being continuously introduced into reaction zone 130. In some embodiments, feed stream 114 and feed stream 118 are independently cooled to a temperature of 0°C to -85°C, such as 0°C to -80°C, 0°C to -75°C, 0°C to -70°C, 0°C to -65°C, 0°C to -60°C, 0°C to -55°C, 0°C to -50°C, 0°C to -45°C, 0°C to -40°C, 0°C to -35°C, 0°C to -30°C, 0°C to -25°C, 0°C to -20°C, 0°C to -15°C, or 0°C to -10°C before being continuously introduced into reaction zone 130. In an embodiment, feed stream 114 and feed stream 118 are independently cooled to a temperature of -20°C to -80°C, such as -30°C to -70°C, -35°C to -65°C, -40°C to -60°C, or -45°C to -55°C, prior to being continuously introduced into reaction zone 130. Without being bound by theory, it is believed that the addition of the organolithium reagent to reaction zone 130 causes an exothermic reaction, necessitating the system be cooled to a suitable temperature to avoid dispersion of one or more of the reactions that occur when the contents are introduced into reaction zone 130 at a temperature outside of the described suitable range. As previously described, the contents entering reaction zone 130 can be cooled by any suitable cooling device, such as heat exchanger 150.

[0034] According to an embodiment, the content of the second reagent feed tank 140 includes an organolithium reagent. In an embodiment, the organolithium reagent initially present in the second reagent feed tank 140 in the system can include any suitable organolithium reagent. Examples of suitable organolithium reagents can include but are not limited to n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium or a combination thereof. In certain embodiments, the organolithium reagent initially present in the second reagent feed tank 140 is n-butyl lithium.

[0035] Optionally, an amount of solvent may be added to the second reagent feed tank 140 and / or at any point along the second reagent feed stream 116 to dilute the organolithium reagent being fed to the heat exchanger 150. Once the second reagent feed stream 116 passes through the heat exchanger 150, it is fed to the reaction zone 130 via the cooled feed stream 118, which fluidly couples the heat exchanger 150 to the reaction zone 130. In embodiments, the solvent is an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

[0036] If excess organolithium reagent passes through the second reagent feed stream 116 and is distributed to other components of the system (such as reaction zone 130), a quench tank 122 containing a quenching agent such as ammonium chloride may be optionally provided at any point along the second reagent feed stream 116, thereby causing a process upset. However, the quench tank 122 is only Figure 1 The catalyst precursor material production system 100 is shown as an optional component and does not affect the purity of the product produced by the catalyst precursor material production system 100. It should be understood that in some embodiments, a quenching agent can be added to any component of the precursor material production system 100 (e.g., precooler 120, heat exchanger 150, or reaction zone 130) as needed to quench the reaction. However, some embodiments do not include quenching.

[0037] After the contents of the first reagent feed tank 110 and the second reagent feed tank 140 have been continuously added to the reaction zone 130, the contents of the reaction zone 130 are mixed to produce a catalyst precursor material 160. The conditions of the reaction zone 130 are maintained at a temperature of 0°C to -90°C, and the residence time of its contents in the reaction zone 130 is 0.1 seconds to 120 minutes. Without being bound by theory, it is believed that the temperature range of the reaction zone 130 allows the catalyst precursor material 160 produced by such a method to produce the desired product. Suitable reaction zone 130 equipment may include, but is not limited to, a tubular reactor or a stirred tank reactor. In an embodiment, the catalyst precursor material production system 100 may further include a nitrogen blanket, one or more thermocouples and / or a sampling port.

[0038] In an embodiment, reaction zone 130 is cooled during the continuous addition of any of the contents of first reagent feed tank 110 and / or second reagent feed tank 140. In an embodiment, the temperature of reaction zone 130 during the continuous introduction of the contents is 0°C to -90°C and all ranges and sub-ranges therebetween. In an embodiment, the temperature of reaction zone 130 is -5°C to -90°C, such as -10°C to -90°C, -15°C to -90°C, -20°C to -90°C, -25°C to -90°C, -30°C to -90°C, -35°C to -90°C, -40°C to -90°C, -45°C to -90°C, -50°C to -90°C, -55°C to -90°C, -60°C to -90°C, -65°C to -90°C, -70°C to -90°C, -75°C to -90°C, -80°C to -90°C or -85°C to -90°C. In some embodiments, the temperature of reaction zone 130 is 0°C to -85°C, such as 0°C to -80°C, 0°C to -75°C, 0°C to -70°C, 0°C to -65°C, 0°C to -60°C, 0°C to -55°C, 0°C to -50°C, 0°C to -45°C, 0°C to -40°C, 0°C to -35°C, 0°C to -30°C, 0°C to -25°C, 0°C to -20°C, 0°C to -15°C, or 0°C to -10°C. In embodiments, the temperature of reaction zone 130 is -20°C to -80°C, such as 30°C to -70°C, -35°C to -65°C, -40°C to -60°C, or -45°C to -55°C. Without being bound by theory, it is believed that the described temperature ranges of reaction zone 130 allow for the production of suitable catalyst precursor materials. Reaction zone 130 can be cooled by any suitable means.

[0039] Based on the previously described embodiments, the residence time of the contents in reaction zone 130 can be in the range of 0.1 seconds to 120 minutes, and all ranges and sub-ranges therebetween. Here, the term "residence time" is defined as the average time that any one or more contents remain in the reaction zone. The residence time is measured by dividing the reaction zone volume by the total volume flow rate of any one or more of the one or more contents in the reaction zone. In embodiments, the residence time of the contents in reaction zone 130 ranges from 1 second to 120 minutes, 10 seconds to 120 minutes, 30 seconds to 120 minutes, 1 minute to 120 minutes, 5 minutes to 110 minutes, 10 minutes to 100 minutes, 20 minutes to 90 minutes, 25 minutes to 75 minutes, 30 minutes to 70 minutes, 35 minutes to 65 minutes, 40 minutes to 60 minutes, 0.1 seconds to 30 minutes, 0.1 seconds to 10 minutes, 0.1 seconds to 5 minutes, 0.1 seconds to 1 minute, 0.1 seconds to 30 seconds, 1 second to 10 minutes, 1 second to 5 minutes, 1 second to 1 minute, or 1 second to 30 seconds. In some embodiments, the residence time of the contents in reaction zone 130 ranges from 0.1 seconds to 30 seconds, such as 0.1 seconds to 25 seconds, 0.1 seconds to 20 seconds, 0.1 seconds to 15 seconds, 0.1 seconds to 10 seconds, 0.1 seconds to 5 seconds, 0.1 seconds to 1 second, or 0.1 seconds to 0.5 seconds.

[0040] The reaction between the dihalo-substituted Group 14 metal, haloalkane, and organolithium in reaction zone 130 is exothermic. Therefore, in some embodiments, the mixture of dihalo-substituted Group 14 metal and / or organolithium can be optionally quenched with any suitable quenching agent in reaction zone 130. However, quenching any of the components in reaction zone 130 is not a required step in the method for producing the catalyst precursor material of the embodiments.

[0041] Reference now Figure 2 , describe additional systems and methods for producing catalyst precursor materials by introducing a continuous flow stream into a reaction zone. Figure 2 In the embodiment of the catalyst precursor material production system 300 shown, the contents of the first reagent feed tank 310 are introduced into an optional heat exchanger 320 by a first reagent feed stream 312, which couples the first reagent feed tank 310 with an optional heat exchanger 320 fluid. The first reagent feed tank 310 may include any suitable storage device, such as a cooling container, optionally with the ability to mix any of its contents. It should be further understood that the first reagent feed tank 310 and the optional heat exchanger 320 may be a single, combined physical unit or a separate physical unit fluidly coupled to each other.

[0042] Heat exchanger 320 can be optionally added anywhere along first reagent feed stream 312 to cool the contents of first reagent feed tank 310 before its contents are introduced into first reaction zone 330 via cooled first reagent feed stream 314. According to an embodiment, the contents of first reagent feed tank 310 can contain an organolithium reagent, optionally in a solvent. Heat exchanger 320 can be any heat exchanger capable of reducing first reagent feed stream 312 to a temperature from 0°C to -90°C.

[0043] In an embodiment, the organolithium reagent initially present in the first reagent feed tank 310 in the system may include any suitable organolithium reagent. Examples of suitable organolithium reagents may include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, or a combination thereof. In certain embodiments, the organolithium reagent initially present in the first reagent feed tank 310 is n-butyllithium.

[0044] Optionally, an amount of solvent may be added to the first reagent feed tank 310 and / or at any point along the first reagent feed stream 312 and / or at any point along the cooled first reagent feed stream 314 to dilute the organolithium reagent fed to the first reaction zone 330. In an embodiment, the solvent is an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

[0045] At the same time, the contents of the second reagent feed tank 340 are fed by the second reagent feed stream 316 through an optional heat exchanger 350, which couples the second reagent feed tank 340 fluid to the optional heat exchanger 350. The second reagent feed tank 340 can include any suitable storage device, such as a cooling container, optionally with the ability to mix any of its contents. It should be further understood that the second reagent feed tank 340 and the optional heat exchanger 350 can be a single, combined physical unit or a separate physical unit.

[0046] The optional heat exchanger 350 can be optionally added anywhere along the second reagent feed stream 314 to cool the contents of the second reagent feed tank 340 to a temperature in the range of 0°C to -90°C before its contents are introduced into the first reaction zone 330 by the cooled second reagent feed stream 318. According to an embodiment, the contents of the second reagent feed tank 340 can contain halogenated alkanes, optionally in a solvent. Optionally, an amount of solvent can be added to the second reagent feed tank 340 and / or at any point along the second reagent feed stream 314 and / or at any point along the cooled second reagent feed stream 316 to dilute the halogenated alkanes fed to the first reaction zone 330.

[0047] In an embodiment, the halogenated alkane initially present in the second reagent feed tank 340 in the system 300 can include any suitable halogenated alkane, such as dihalomethane. Examples of suitable dihalomethanes include but are not limited to dibromomethane, dichloromethane, difluoromethane, diiodomethane, bromochloromethane, bromofluoromethane, bromoiodomethane, chlorofluoromethane, chloroiodomethane, fluoroiodomethane or a combination thereof. In certain embodiments, the halogenated alkane initially present in the second reagent feed tank 340 is bromochloromethane.

[0048] Prior to being continuously introduced into the first reaction zone 330, the contents of the first reagent feed tank 310 and optionally the second reagent feed tank 340 are cooled to a temperature of 0° C. to −90° C. In an embodiment, the contents of the first reagent feed tank 310 and optionally the second reagent feed tank 340 are cooled to a temperature of −5° C. to −90° C., such as −10° C. to −90° C., −15° C. to −90° C., −20° C. to −90° C., −25° C. to −90° C., −30° C. to −90° C., −35° C. to −90° C., −40° C. to −90° C., −45° C. to −90° C., −50° C. to −90° C., −55° C. to −90° C., −60° C. to −90° C., −65° C. to −90° C., −70° C. to −90° C., −75° C. to −90° C., −80° C. to −90° C., or −85° C. to −90° C. In some embodiments, the contents of the first reagent feed tank 310 and optionally the second reagent feed tank 340 are cooled to a temperature of 0°C to -85°C, such as 0°C to -80°C, 0°C to -75°C, 0°C to -70°C, 0°C to -65°C, 0°C to -60°C, 0°C to -55°C, 0°C to -50°C, 0°C to -45°C, 0°C to -40°C, 0°C to -35°C, 0°C to -30°C, 0°C to -25°C, 0°C to -20°C, 0°C to -15°C or 0°C to -10°C. In an embodiment, the contents of the first reagent feed tank 310 and optionally the second reagent feed tank 340 are cooled to a temperature of -20°C to -80°C, such as -30°C to -70°C, -35°C to -65°C, -40°C to -60°C or -45°C to -55°C. Without being bound by theory, it is believed that the addition of the organolithium reagent to the first reaction zone 330 causes an exothermic reaction, necessitating the cooling of the system to a suitable temperature to avoid dispersion of one or more of the reactions that occur when the contents are introduced to the first reaction zone 330 at a temperature outside of the described suitable range. As previously described, the contents entering the first reaction zone 330 can be cooled by any suitable cooling device, such as a heat exchanger.

[0049] Once the contents of the first reagent feed tank 310 and the second reagent feed tank 340 are introduced into the first reaction zone 330, it is believed that the organolithium reagent lithiates the halogenated alkane in a lithiation reaction. Without being bound by theory, it is believed that lithiating the halogenated alkane in the first reaction zone 330 can increase the yield of the alkane. Figure 2The catalyst precursor material production system 300 is shown to produce catalyst precursor material with a higher purity and yield.

[0050] After the contents of the first reagent feed tank 310 and the second reagent feed tank 340 have been introduced into the first reaction zone 330, the contents of the first reaction zone 330 are mixed to produce an intermediate catalyst precursor material 326. The conditions of the first reaction zone 330 are maintained at a temperature of 0°C to -90°C, and the residence time of its contents in the first reaction zone 330 is 0.1 seconds to 120 minutes. Without being bound by theory, it is believed that the temperature range of the first reaction zone 330 allows the intermediate catalyst precursor material 326 produced by such a method to produce a desired final product. Suitable first reaction zone 330 equipment may include but is not limited to a tubular reactor or a stirred tank reactor. In an embodiment, the catalyst precursor material production system 300 may further include a nitrogen blanket, one or more thermocouples and / or a sampling port.

[0051] Once the catalyst precursor material 326 has been produced and cooled to a suitable temperature, the catalyst precursor material is then introduced into the second reaction zone 380. In embodiments, the conditions in the second reaction zone 380 are the same as the first reaction zone 330. In other embodiments, the conditions in the second reaction zone 380 are different than the first reaction zone 330.

[0052] At the same time, the contents of the third reagent feed tank 360 are fed by the third reagent feed stream 322 through an optional heat exchanger 370, and the second reagent feed stream couples the third reagent feed tank 360 fluid to the optional heat exchanger 370. The third reagent feed tank 360 can include any suitable storage device, such as a cooling container, optionally with the ability to mix any of its contents. It should be further understood that the third reagent feed tank 360 and the optional heat exchanger 370 can be a combined physical unit or a separate physical unit.

[0053] An optional heat exchanger 370 may be added anywhere along the second reagent feed stream 322 to cool the contents of the third reagent feed tank 360 to a temperature of 0°C to -90°C before its contents are introduced into the second reaction zone 370 by the cooled third reagent feed stream 324. According to an embodiment, the contents of the third reagent feed tank 360 may contain a dihalogen-substituted Group 14 metal, optionally in a solvent. Optionally, an amount of solvent may be added to the third reagent feed tank 360 and / or at any point along the third reagent feed stream 322 and / or at any point along the cooled third reagent feed stream 324 to dilute the dihalogen-substituted Group 14 metal fed to the second reaction zone 380.

[0054] In an embodiment, the dihalo-substituted Group 14 metal may include, but is not limited to, dichlorodiisopropylsilane, di-tert-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-tert-butyldichlorogermane, dichlorodiphenylgermane, or a combination thereof. In certain embodiments, the dihalo-substituted Group 14 metal is dichlorodiisopropylsilane.

[0055] It should be understood that the concentration of the various components in the first reagent feed tank 310 and / or the second reagent feed tank 340 can be modified by adding solvent at any point before adding the first reagent feed stream 314 and / or the second reagent feed stream 318 to the first reaction zone 330, or adding solvent at any point before adding the precursor vapor 326 to the second reaction zone 380. Similarly, the concentration of the components in the third reagent feed tank 360 can be modified by adding solvent at any point before the reagent feed stream 324 is added to the second reaction zone 380. Without being bound by theory, it is believed that if the concentration of the dihalo-substituted Group 14 metal and / or the haloalkane is too high or too low, it will have a negative impact on the dilution of the components, the control of the reaction rate, the mixing control, and the system temperature maintenance.

[0056] In an embodiment, first reaction zone 330 and / or second reaction zone 380 are cooled during the described process. In an embodiment, the temperature of first reaction zone 330 and / or second reaction zone 380 during the continuous introduction of the contents is from 0°C to -90°C and all ranges and sub-ranges therebetween. In an embodiment, the temperature of the first reaction zone 330 and / or the second reaction zone 380 is -5°C to -90°C, such as -10°C to -90°C, -15°C to -90°C, -20°C to -90°C, -25°C to -90°C, -30°C to -90°C, -35°C to -90°C, -40°C to -90°C, -45°C to -90°C, -50°C to -90°C, -55°C to -90°C, -60°C to -90°C, -65°C to -90°C, -70°C to -90°C, -75°C to -90°C, -80°C to -90°C or -85°C to -90°C. In some embodiments, the temperature of the first reaction zone 330 and / or the second reaction zone 380 is 0° C. to -85° C., such as 0° C. to -80° C., 0° C. to -75° C., 0° C. to -70° C., 0° C. to -65° C., 0° C. to -60° C., 0° C. to -55° C., 0° C. to -50° C., 0° C. to -45° C., 0° C. to -40° C., 0° C. to -35° C., 0° C. to -30° C., 0° C. to -25° C., 0° C. to -20° C., 0° C. to -15° C., or 0° C. to -10° C. In an embodiment, the temperature of the first reaction zone 330 and / or the second reaction zone 380 is -20° C. to -80° C., such as 30° C. to -70° C., -35° C. to -65° C., -40° C. to -60° C., or -45° C. to -55° C. Without being bound by theory, it is believed that the temperature ranges described for the first reaction zone 330 and / or the second reaction zone 380 allow the catalyst precursor material produced by the methods described herein to produce the desired products. The first reaction zone 330 and / or the second reaction zone 380 may be cooled by any suitable means.

[0057] Based on the previously described embodiments, the residence time of the contents in the first reaction zone 330 and / or the second reaction zone 380 can be in the range of 0.1 seconds to 120 minutes, and all ranges and sub-ranges therebetween. Herein, the term "residence time" is defined as the average time that a fluid stream remains in the first reaction zone 330 and / or the second reaction zone 380. The residence time is measured by dividing the reaction zone volume by the total volume flow rate of the fluid in the reaction zone. In an embodiment, the residence time of the contents in the first reaction zone 330 and / or the second reaction zone 380 ranges from 1 second to 120 minutes, 10 seconds to 120 minutes, 30 seconds to 120 minutes, 1 minute to 120 minutes, 5 minutes to 110 minutes, 10 minutes to 100 minutes, 20 minutes to 90 minutes, 25 minutes to 75 minutes, 30 minutes to 70 minutes, 35 minutes to 65 minutes, 40 minutes to 60 minutes, 0.1 seconds to 30 minutes, 0.1 seconds to 10 minutes, 0.1 seconds to 5 minutes, 0.1 seconds to 1 minute, 0.1 seconds to 30 seconds, 1 second to 10 minutes, 1 second to 5 minutes, 1 second to 1 minute or 1 second to 30 seconds. In some embodiments, the residence time of the contents in the first reaction zone 330 and / or the second reaction zone 380 ranges from 0.1 seconds to 30 seconds, such as 0.1 seconds to 25 seconds, 0.1 seconds to 20 seconds, 0.1 seconds to 15 seconds, 0.1 seconds to 10 seconds, 0.1 seconds to 5 seconds, 0.1 seconds to 1 second, or 0.1 seconds to 0.5 seconds.

[0058] The reaction between the dihalo-substituted Group 14 metal, haloalkane and organolithium in the second reaction zone 380 is exothermic. Therefore, in some embodiments, the mixture in the second reaction zone 380 can be optionally quenched with a suitable quenching agent. However, in the method for forming the catalyst precursor material of the embodiment, quenching any of the components in the second reaction zone 380 is not a necessary step.

[0059] Further, if an excess of dihalo-substituted Group 14 metal and / or organolithium reagent is passed through system 300, a quench tank ( ) containing a quenching agent, such as ammonium chloride, may optionally be provided at any point in catalyst precursor material production system 300. Figure 2 However, the quench tank is only Figure 2 The optional components in the catalyst precursor material production system 300 are shown and do not affect the purity of the catalyst precursor material 390 produced by the catalyst precursor material production system 300.

[0060] The method described herein is applicable to the preparation of various catalyst precursor materials, which are used to prepare catalysts that contribute to the production of linear low-density ethylene-based polymers. Such catalysts are described in detail in WO 2018 / 022975 and WO 2018 / 083056, which are incorporated herein by reference.

[0061] As an example but not limited to, according to the embodiments, the catalyst precursor material can be used to produce a representative catalyst as shown in formula (I):

[0062]

[0063] In embodiments of formula (I), M is titanium, zirconium or hafnium, each independently in a formal oxidation state of +2, +3 or +4; X is a Group 14 metal; R1 is isopropyl, tert-butyl or hexyl; and R2 is isopropyl, tert-butyl or hexyl. In embodiments, R1 and R2 are the same as each other. In other embodiments, R1 and R2 are different from each other.

[0064] According to the examples, formula (I) merely illustrates the catalysts that can be prepared from various catalyst precursor materials. It does not limit the scope of the catalysts that can be prepared from the various catalyst precursor materials described herein.

[0065] Examples

[0066] The embodiments are further illustrated by the following examples.

[0067] Example 1

[0068] Load 187 grams (g) of dichlorodiisopropylsilane (DCDIS), 388g of bromochloromethane (BCM) and 1,781g of tetrahydrofuran (THF) to the first reagent feed tank and mix under nitrogen (N2) layer.The first reagent feed tank is connected to precooler by pipeline.800 milliliters (mL) of 1.6 moles (M) of hexane are introduced into pipeline.The content in the vacuum-propelled pipeline crosses the first heat exchanger (that is, the coil in the bathtub full of dry ice and acetone) and enters the precooler with a flow rate of 1.2mL per minute (1.2 milliliters / minute).Once the content in the pipeline is introduced into the precooler, the agitator in the precooler begins to mix its content with 740 revolutions per minute (rpm).After the precooler reaches the capacity of its expectation, its content is introduced into reaction zone by other pipeline, and the pipeline fluid connects precooler and reaction zone.

[0069] Once the precooler begins to flow into the reaction zone, the agitator in the reaction zone begins to mix the introduced contents at 740 rpm. When the temperature in the reaction zone reaches -75 ° C, n-butyl lithium (n-BuLi) is introduced into the reaction zone from the second reagent feed tank at a flow rate of 0.71 ml / min after being cooled by the second heat exchanger. The second reagent feed tank is connected to the reaction zone fluid using a pipeline. During the catalyst precursor material synthesis duration, the temperature in the reaction zone is maintained at about -70 ° C.

[0070] The average residence time of the contents of the reaction zone before being collected in the product container was 50 minutes. The reaction zone operation - and collection of catalyst precursor material - continued for 30 hours. After 30 hours, the n-butyl lithium was transferred to the quench tank and the lines were flushed with hexane to clear any residual lithiated species in the system.

[0071] The conditions used for the continuous synthesis of catalyst precursor materials are provided in Table 1:

[0072] Table 1

[0073] parameter value Dwell time 50 minutes DCDIS concentration 8wt.% BCM is equivalent to DCDIS 3.0 n-Butyl lithium is equivalent to DCDIS 2.5 Reaction zone temperature -70℃ Reaction zone volume 100mL

[0074] Three samples were collected during the 30 hour operation period. The purity of each sample was tested using a gas chromatograph (GC). Specifically, the purity of the sample was calculated by measuring the ratio of the GC area of ​​the desired product to any undesirable product. The purity of each sample in these samples is provided in Table 2:

[0075] Table 2

[0076] Sample source GC purity S1: Reaction zone (8th hour) 96.62％ S2: Product container 1 (collected in the first 20 hours) 64.55％ S3: Product container 2 (collected in the last 10 hours) 93.29％

[0077] The first sample (S1) was taken directly from the reaction zone after eight hours of continuous operation, which showed high purity to confirm the production of the described catalyst precursor material. Figure 3 The purity was 96.62%.

[0078] The second sample (S2) was taken from the first product container which contained catalyst precursor material produced during the first 20 hours of operation. A GC sample of the S2 production indicated a purity of 64.55%.

[0079] The third sample (S3) was taken from the second product container which contained the catalyst precursor material produced during the last 10 hours of operation. A GC sample of the S3 production indicated a purity of 93.29%.

[0080] Overall, the cumulative purity of the collected catalyst precursor material samples was calculated to be 81.84%.

[0081] However, the purity of catalyst precursor material S3 increased by 28.74% from the 20th hour to the 30th hour. This trend of increasing purity indicates that, according to the embodiments described herein, the longer the system is continuously used, the purer the catalyst precursor material becomes. Therefore, the results confirm that the system described in the present disclosure is suitable for producing catalyst precursor materials in a continuous flow reaction.

[0082] Example 2

[0083] The first reagent stream is produced by precooling a mixture of chloroiodomethane (CIM) and THF to -50°C. Simultaneously, a second reagent stream of 2.5M n-butyl lithium in hexane is precooled to -50°C. Precooling is achieved by a separate heat exchanger (i.e., the pipe is inserted into a circulating bath with cooling silicone oil) and deposited into the first reaction zone, where the mixing lasts from 0.15 seconds to 0.3 seconds before being discharged into the second reaction zone. A third reagent stream containing DCDIS and THF is precooled to -50°C with a heat exchanger. The third reagent stream is then discharged into the second reaction zone, where its contents are mixed with the contents of the first reaction zone.

[0084] The conditions used for the continuous synthesis of catalyst precursor materials are provided in Table 3:

[0085] Table 3

[0086] parameter value Residence time in the first reaction zone 0.15 seconds to 0.3 seconds Total flow rate 56 ml per minute CIM is equivalent to DCDIS 6.75 n-Butyl lithium is equivalent to DCDIS 2.25 temperature -50℃ Second reaction zone pressure 200 pounds per square inch

[0087] During the 6-hour operation period, two samples were collected using the parameters specified above. The purity of the samples was tested using a gas chromatograph (GC). Specifically, the purity of the sample was calculated by measuring the ratio of the GC area of ​​the desired product to any undesired product. The results of the samples are provided in Table 4 below:

[0088] Table 4

[0089] parameter result Purity of sample 1 94％ Purity of sample 2 85％ Isolated product yield 71％

[0090] Thus, the results confirm that the system described in this disclosure is suitable for producing catalyst precursor materials in a continuous flow reaction.

[0091] In a first aspect of the present disclosure, a method comprises: reacting an organic lithium reagent, a haloalkane, and at least one solvent in a first reaction zone to form a first solution; continuously adding the first solution and a second solution to a second reaction zone, wherein the second solution comprises a dihalo-substituted Group 14 metal and at least one solvent; and mixing the first solution and the second solution in the second reaction zone.

[0092] A second aspect of the present disclosure may include the first aspect, further comprising separately cooling the organolithium reagent and the halogenated alkane of the first solution to a temperature of 0°C to -90°C before continuously adding the first solution to the first reaction zone.

[0093] The third aspect of the present disclosure may include the first aspect or the second aspect, wherein the dihalo-substituted Group 14 metal comprises dichlorodiisopropylsilane, di-tert-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-tert-butyldichlorogermane, dichlorodiphenylgermane or a combination thereof.

[0094] The fourth aspect of the present disclosure may include any of the first to third aspects, wherein the organic lithium reagent includes n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, or a combination thereof.

[0095] The fifth aspect of the present disclosure may include any of the first to fourth aspects, wherein the halogenated alkane comprises a dihalogenated methane, preferably bromochloromethane or chloroiodomethane.

[0096] The sixth aspect of the present disclosure may include any of the first to fifth aspects, wherein the at least one solvent comprises an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

[0097] The seventh aspect of the present disclosure may include any of the first to sixth aspects, wherein the at least one solvent comprises tetrahydrofuran, hexane, or a combination thereof.

[0098] An eighth aspect of the present disclosure may include any of the first to seventh aspects, wherein the first solution is cooled to a temperature of 0°C to -90°C before continuously adding the first solution to the second reaction zone.

[0099] A ninth aspect of the present disclosure may include any of the first to eighth aspects, wherein the temperature of the first reaction zone and the second reaction zone is -40°C to -70°C.

[0100] In the tenth aspect of the present disclosure, a method comprises: mixing a first solution in a first reaction zone, the first solution comprising a halogenated alkane, at least one solvent and a first component selected from a dihalide-substituted Group 14 metal or an organic lithium reagent; continuously adding the first solution to a second reaction zone; continuously adding a second solution to the second reaction zone, the second solution comprising at least one solvent and a second component selected from the dihalide-substituted Group 14 metal or the organic lithium reagent, wherein the second component is different from the first component; and mixing the first solution and the second solution in the second reaction zone.

[0101] An eleventh aspect of the present disclosure encompasses the tenth aspect, wherein the first component is the dihalo-substituted Group 14 metal, and the second component is the organolithium reagent.

[0102] A twelfth aspect of the present disclosure includes the tenth aspect, wherein the first component is the organolithium reagent, and the second component is the dihalo-substituted Group 14 metal.

[0103] The thirteenth aspect of the present disclosure includes any of the tenth to twelfth aspects, wherein the dihalo-substituted Group 14 metal comprises dichlorodiisopropylsilane, di-tert-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-tert-butyldichlorogermane, dichlorodiphenylgermane, or a combination thereof.

[0104] A fourteenth aspect of the present disclosure includes any of the tenth to thirteenth aspects, wherein the organic lithium reagent includes n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, or a combination thereof.

[0105] A fifteenth aspect of the present disclosure includes any of the tenth to fourteenth aspects, wherein the halogenated alkane comprises a dihalomethane, preferably chloroiodomethane or bromochloromethane.

[0106] A sixteenth aspect of the present disclosure includes any of the tenth to fifteenth aspects, wherein the at least one solvent comprises an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

[0107] A seventeenth aspect of the present disclosure includes any of the tenth to sixteenth aspects, wherein the at least one solvent comprises tetrahydrofuran, hexane, or a combination thereof.

[0108] An eighteenth aspect of the present disclosure includes any of the tenth to seventeenth aspects, wherein the first solution and the second solution are cooled to at least -70°C before continuously adding the first solution and the second solution to a reaction zone.

[0109] A nineteenth to eighteenth aspects of the present disclosure include any of the tenth to eighteenth aspects, wherein the temperature of the reaction zone is 0°C to -90°C, preferably wherein the temperature of the reaction zone is -40°C to -70°C.

[0110] It will be apparent to those skilled in the art that various modifications and changes may be made to the embodiments described herein without departing from the spirit and scope of the subject matter claimed. Therefore, this specification is intended to cover modifications and changes of the various embodiments described herein, provided that these modifications and changes fall within the scope of the appended claims and their equivalents.

Claims

1. A method for preparing a catalyst precursor in a continuous flow reaction, comprising: mixing a first solution in a first reaction zone, the first solution comprising a haloalkane, at least one solvent, and a first component selected from one of a dihalo-substituted Group 14 metal or an organolithium reagent; continuously adding the first solution to a second reaction zone and simultaneously continuously adding a second solution to the second reaction zone, the second solution comprising at least one solvent and a second component selected from one of the dihalo-substituted Group 14 metal or the organolithium reagent, wherein the second component is different from the first component; and The first solution and the second solution are mixed in the second reaction zone.

2. The method of claim 1, wherein the first component is the dihalo-substituted Group 14 metal and the second component is the organolithium reagent.

3. The method of claim 1, wherein the first component is the organolithium reagent and the second component is the dihalo-substituted Group 14 metal.

4. The method of any one of the preceding claims, wherein the dihalo-substituted Group 14 metal comprises dichlorodiisopropylsilane, di-tert-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-tert-butyldichlorogermane, dichlorodiphenylgermane, or a combination thereof.

5. The method of any one of the preceding claims, wherein the organolithium reagent comprises n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, or a combination thereof.

6. A method according to any one of the preceding claims, wherein the haloalkane comprises a dihalomethane.

7. The process according to any one of the preceding claims, wherein the temperature of the first reaction zone, the second reaction zone, or both, is from 0°C to -90°C.

8. The method of claim 6, wherein the dihalomethane comprises chloroiodomethane.

9. The process of claim 7, wherein the temperature of the first reaction zone, the second reaction zone, or both is from -40°C to -70°C.

10. A method for preparing a catalyst precursor in a continuous flow reaction, comprising: reacting an organolithium reagent, a haloalkane, and at least one solvent in a first reaction zone to form a first solution; adding the first solution and a second solution simultaneously and continuously to a second reaction zone, wherein the second solution comprises a dihalo-substituted Group 14 metal and at least one solvent; and The first solution and the second solution are mixed in the second reaction zone.

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