Ziegler-natta catalysts with electron donor compounds for increasing polymer molecular weight

Abstract

The heterogeneous procatalyst includes a preformed heterogeneous procatalyst and a metal-ligand complex. The preformed heterogeneous procatalyst includes a titanium species and a magnesium chloride (MgCl2) support. The metal-ligand complex has the structural formula (L) nM (Y) m (XR2) b, wherein M is a metal cation; each L is a neutral ligand or (= O); each Y is a halide or (C1-C20) alkyl; each XR2 is an anionic ligand wherein X is a heteroatom or a heteroatom-containing functional group, and R2 is a (C1-C20) hydrocarbyl group or a (C1-C20) heterohydrocarbyl group; n is 0, 1 or 2; m is 0 to 4; and b is 1 to 6. The metal-ligand complexes are generally charge neutral. The heterogeneous pre-catalyst exhibits an improved average molecular weight capability. A catalyst system includes the heterogeneous pre-catalyst and a co-catalyst. Also disclosed are methods for producing the heterogeneous pre-catalyst and methods for producing ethylene-based polymers using the heterogeneous pre-catalyst.

Description

[0001] This application is a divisional application of Chinese patent application No. 201980040682.X (filed on May 29, 2019, entitled "Ziegler-Natta Catalyst with Electron Donor Compound for Increasing Polymer Molecular Weight").

[0002] Cross-reference to related applications

[0003] This application claims priority to U.S. Provisional Application No. 62 / 679,263, filed June 1, 2018, which is incorporated herein by reference in its entirety. Technical Field

[0004] The embodiments of this disclosure generally relate to Ziegler-Natta catalysts that can be used for olefin polymerization. More specifically, the embodiments of this disclosure relate to Ziegler-Natta catalysts for producing ethylene-based polymers having increased molecular weight and high-density fractions. Background Technology

[0005] Polyethylene polymers are among the most common plastics and can be used in a variety of ways depending on their structure, such as as bags / liners, caps / lids, sanitary films, industrial injection molding, etc. It is estimated that approximately 80 million metric tons of ethylene-based polymers are produced annually. Due to the need for significantly and continuously differentiated polymer products in the polyethylene market, researchers have devoted considerable effort to finding methodological changes that will yield these new products.

[0006] For many polyethylene polymers and copolymers, such as LLDPE, ethylene is typically copolymerized with short-chain olefin comonomers (e.g., 1-butene, 1-hexene, and / or 1-octene). The resulting polyethylene polymer is essentially linear but includes a significant number of short branches, and these characteristics give it higher tensile strength, higher impact strength, and higher puncture resistance compared to low-density polyethylene (LDPE). These improved properties, in turn, mean that films of lower thickness (gauge) can be manufactured, and the products exhibit improved resistance to environmental stress cracking. LLDPE is primarily used in membrane applications due to its toughness, flexibility, and relative transparency. Examples of products range from agricultural films, food protective packaging, and bubble wrap to multilayer and composite films.

[0007] Ziegler-Natta catalysts have been used for many years to produce various polyethylenes, including LLDPE. These catalysts typically comprise a magnesium halide support and at least one transition metal compound, typically titanium. Despite their effectiveness, the molecular weight capability of these catalysts is generally limited, especially at high polymerization temperatures. Furthermore, it is difficult to tune the composition of polymers produced using Ziegler-Natta catalysts. Summary of the Invention

[0008] Therefore, there is a persistent need for processes, catalyst compositions, and methods for producing novel, differentiated LLDPE polymers. In particular, there is a persistent need for processes, catalyst compositions, and methods for producing ethylene-based polymers with increased weight-average molecular weight (Mw), increased high-density fraction (HDF), and / or decreased comonomer weight percentage. This disclosure relates to heterogeneous pre-catalysts and catalyst systems, and methods and processes utilizing these heterogeneous pre-catalysts and catalyst systems to produce ethylene-based polymers with increased Mw and HDF and decreased comonomer weight percentage.

[0009] According to at least one embodiment, the heterogeneous precatalyst comprises a titanium material with a specific surface area of ​​at least 100 m². 2 / g of pre-formed magnesium chloride (MgCl2) carrier and Al(Cl) structural formula x (R 1 ) 3-x Or Si(Cl) y (R 1 ) 4-y Chlorinating agent, of which R 1 For (C1-C 30 The catalyst may contain a hydrocarbon group; x is 1, 2, or 3; and y is 1, 2, 3, or 4. The heterogeneous pre-catalyst may also include a component with the structural formula (L). n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl, each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ( ) Heteroalkyl group; n is 0, 1 or 2; m is 0, 1, 2, 3 or 4; b is 1, 2, 3, 4, 5 or 6; and the metal-ligand complex is generally charge-neutral.

[0010] According to at least another embodiment, the heterogeneous precatalyst may include a pre-shaped heterogeneous precatalyst and a metal-ligand complex. The pre-shaped heterogeneous precatalyst may include a titanium material and a MgCl2 support. The metal-ligand complex may have the structural formula (L). n M(Y) m (XR 2 ) b Where M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 The metal-ligand complex is generally charge-neutral. In some embodiments, the catalyst system for olefin polymerization may include a heterogeneous pre-catalyst and a co-catalyst comprising an organoaluminum compound.

[0011] According to other embodiments, the catalyst system for olefin polymerization may include a pre-formed heterogeneous pre-catalyst, a metal-ligand complex, and a co-catalyst comprising an organoaluminum compound. The pre-formed heterogeneous pre-catalyst may include a titanium material and a MgCl2 support. The metal-ligand complex may have the structural formula (L). n M(Y) m (XR 2 ) b Where M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ( ) Heteroalkyl group; n is 0, 1 or 2; m is 0, 1, 2, 3 or 4; b is 1, 2, 3, 4, 5 or 6; and the metal-ligand complex is generally charge-neutral.

[0012] According to other embodiments, a method for preparing a heterogeneous pre-catalyst may include contacting a magnesium chloride component with a chlorinating agent, a titanium substance, and a metal-ligand complex. The magnesium chloride component may have a specific surface area of ​​at least 100 m². 2 / g of pre-formed MgCl2 carrier. The chlorinating agent may have the structural formula Al(Cl). x (R 1 ) 3-x Or Si(Cl) y (R 1 ) 4-y , where R 1 For (C1-C 30 (L) Hydrocarbon group; x is 1, 2, or 3; and y is 1, 2, 3, or 4. Metal-ligand complexes may have the structural formula (L). n M(Y) m (XR 2 ) b Where M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C)20 )alkyl; each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ( ) Heteroalkyl group; n is 0, 1 or 2; m is 0, 1, 2, 3 or 4; b is 1, 2, 3, 4, 5 or 6; and the metal-ligand complex is generally charge-neutral.

[0013] According to other embodiments, the method for preparing the heterogeneous precatalyst may include contacting components (1) and (2) without additional chlorination. Component (1) may be a preformed heterogeneous precatalyst comprising a titanium material and a MgCl2 support. Component (2) may be a material having the structural formula (L). n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ( ) Heteroalkyl group; n is 0, 1 or 2; m is 0, 1, 2, 3 or 4; b is 1, 2, 3, 4, 5 or 6; and the metal-ligand complex is generally charge-neutral.

[0014] Additional features and advantages will be set forth in the following detailed description and will in part become apparent to those skilled in the art from the described embodiments or will be recognized by practice of the embodiments described herein (including the following detailed description and claims). 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 characteristics of the claimed subject matter. Detailed Implementation

[0015] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers (whether of the same or different types). Therefore, the general term polymer encompasses the term "homopolymer," which is typically used to refer to a polymer prepared from only one type of monomer; and "copolymer," which refers to a polymer prepared from two or more different monomers.

[0016] "Ethylene-based polymers" should be understood to mean polymers comprising more than 50% by weight of units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene-based polymers known in the art include low-density polyethylene (LDPE); linear low-density polyethylene (LLDPE); ultra-low-density polyethylene (ULDPE); very low-density polyethylene (VLDPE); single-point catalytic linear low-density polyethylene, including both linear low-density resins and substantially linear low-density resins (m-LLDPE); medium-density polyethylene (MDPE); and high-density polyethylene (HDPE).

[0017] As used herein, a "solution polymerization reactor" is a vessel for performing solution polymerization, in which ethylene monomers, optionally with comonomers, are polymerized or copolymerized after being dissolved in a non-reactive solvent containing a catalyst. Heat can be removed from or added to the solution polymerization reactor, and subsequently, by connecting the reactor to one or more heat exchangers. High reactor temperatures may be required to keep the polymer in a liquid state. Hydrogen can be used in solution polymerization methods; however, not all solution polymerization methods require hydrogen.

[0018] Ziegler-Natta catalysts are commonly used to produce ethylene-based polymers in copolymerization processes involving copolyethylene and one or more α-olefin comonomers. In these copolymerization processes using typical Ziegler-Natta catalysts, the average molecular weight of the polymer decreases rapidly with increasing polymerization temperature. However, higher polymerization temperatures in solution polymerization processes increase production throughput and produce ethylene-based polymers with desired polymer properties such as excellent optical properties and a dart / tear balance. Increasing the molecular weight capability of Ziegler-Natta catalysts expands their ability to produce novel products and enables polymerization at even higher polymerization temperatures.

[0019] This disclosure relates to Ziegler-Natta type heterogeneous pre-catalysts and catalyst systems exhibiting the ability to increase molecular weight. The catalyst systems disclosed herein may include heterogeneous pre-catalysts and co-catalysts. Heterogeneous pre-catalysts may include titanium materials, pre-shaped magnesium chloride (MgCl2) supports, chlorinating agents, and donor compounds. Donor compounds may have the structural formula (L... n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein: M is a metal cation; each L is a neutral ligand or (=O); Y is a halide or (Cl-C) 20 )alkyl; each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C20 ) hydrocarbon group or (C1-C 20 The complex consists of a heteroalkyl group; n is 0 (zero), 1, or 2; m is 0 (zero), 1, 2, 3, or 4; and b is 1, 2, 3, 4, 5, or 6. The metal-ligand complex can generally be charge-neutral. The preformed MgCl2 support can have a density of at least 100 m² / g (m³). 2 The specific surface area ( / g). The metal-ligand complex donor compound may be incorporated into the heterogeneous pre-catalyst or added to a pre-shaped heterogeneous pre-catalyst to modify the pre-shaped heterogeneous pre-catalyst for the production of a heterogeneous pre-catalyst. In some embodiments, the metal-ligand complex may be incorporated as an external donor into the catalyst system, such that the catalyst system includes the pre-shaped heterogeneous pre-catalyst, a co-catalyst, and the metal-ligand complex.

[0020] A polymerization method is also disclosed, comprising contacting ethylene and optionally one or more α-olefin comonomers with a catalyst system comprising a heterogeneous precatalyst according to embodiments disclosed herein and an optional cocatalyst to form an ethylene-based polymer. Ethylene-based polymers produced in the presence of the catalyst system disclosed herein can exhibit increased molecular weight, increased high-density fractions, and reduced content of optional comonomers.

[0021] In some embodiments, a method for producing a heterogeneous pre-catalyst may include preparing a preformed MgCl2 support, contacting the MgCl2 support with a chlorinating agent to condition the MgCl2 support, contacting the conditioned MgCl2 support with a titanium material, and contacting a slurry comprising the conditioned MgCl2 support and the titanium material with a donor compound. The preformed MgCl2 support may be the reaction product of an alkyl magnesium compound solution in a hydrocarbon diluent with a chloride source. In some embodiments, the hydrocarbon diluent is not separated from the MgCl2 support. In other embodiments, the hydrocarbon diluent may be separated from the MgCl2 support. Preparing the preformed MgCl2 support may include reacting an organomagnesium compound or a complex comprising an organomagnesium compound with a chloride compound such as a metallic or nonmetallic chloride under conditions suitable for producing the preformed MgCl2 support, as described herein. Examples of organomagnesium compounds and / or complexes may include, but are not limited to, C2-C8 alkyl and aryl magnesium, alkylol magnesium and aryl magnesium, carboxylated alkylol magnesium and carboxylated aryl magnesium, or combinations thereof. In some embodiments, the organomagnesium compound may include C2-C8 alkyl magnesium, C1-C8 alkylol magnesium, or combinations thereof. In some embodiments, the organomagnesium compound may be an alkylmagnesium compound, such as butyl ethyl magnesium.

[0022] Organomagnesium compounds or complexes are soluble in hydrocarbon diluents, such as inert hydrocarbon diluents. Examples of hydrocarbon diluents include, but are not limited to, liquefied ethane, propane, isobutane, n-butane, n-hexane, various isohexanes, isooctane, mixtures of alkanes having 5 to 20 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, industrial solvents composed of saturated or aromatic hydrocarbons (such as kerosene, naphtha), and combinations thereof. In some embodiments, the hydrocarbon diluent may be substantially free of any olefin compounds and other impurities. As used herein, the term “substantially free” means that the composition includes less than 0.1 wt% of an ingredient (e.g., impurities, compounds, elements, etc.). In some embodiments, the hydrocarbon diluent may have a boiling point in the range of about -50°C to about 200°C. In some embodiments, the hydrocarbon diluent may include isoparaffin solvents. Examples of isoparaffin solvents include, but are not limited to, ISOPAR, which is available from ExxonMobil. TM Synthetic alkane solvents (e.g., ISOPAR) TM E-chain alkane solvents) and special boiling point (SBP) solvents (e.g., SBP 100 / 140 high-purity dearomatic hydrocarbon solvent) available from Shell Chemicals. Other examples of hydrocarbon diluents may include ethylbenzene, cumene, decahydronaphthalene, and combinations thereof.

[0023] In some embodiments, a method for preparing a preformed MgCl2 support may include dispersing an organomagnesia compound in a hydrocarbon diluent to form a solution or slurry. The concentration of the organomagnesia compound in the hydrocarbon diluent may be sufficient such that, when combined with a chloride compound, the resulting slurry may contain a concentration of organomagnesia compound sufficient to provide efficient production of the MgCl2 support without the use of excessive hydrocarbon diluent. The concentration of the organomagnesia compound should not be so high that the slurry cannot be properly mixed / stirred or fluidized during and after synthesis. The solution or slurry of the organomagnesia compound dispersed in the hydrocarbon diluent may be contacted with a chloride compound to produce the MgCl2 support. The chloride compound may be a metallic or non-metallic chloride. For example, in some embodiments, the chloride compound may be hydrogen chloride gas. In some embodiments, the solution or slurry of the organomagnesia compound and the chloride compound may be contacted at a temperature from -25°C to 100°C or from 0°C to 50°C. In some embodiments, the organomagnesia compound may be contacted with the solution or slurry of the metallic or non-metallic chloride for a period of 1 hour to 12 hours or 4 hours to 6 hours.

[0024] The reaction of chloride compounds with organomagnesium compounds can produce preformed MgCl2 supports, which can be MgCl2 slurries comprising MgCl2 particles dispersed in a hydrocarbon diluent. In some embodiments, the MgCl2 slurry may have an MgCl2 concentration of 0.05 mol / L to 10.0 mol / L or about 0.2 mol / L. The preformed MgCl2 support may have a concentration of at least 100 m... 2 The specific surface area is 1 / g. For example, in some embodiments, the preformed MgCl2 support may have a specific surface area of ​​100m² / g. 2 / g to 1000m 2 / g、200m 2 / g to 800m 2 / g, or 300m 2 / g to 700m 2 / g average surface area.

[0025] In some embodiments, the preformed MgCl2 support can be further processed by heat-treating the preformed MgCl2 support at a temperature of at least 100°C for at least 30 minutes to produce a heat-treated MgCl2 support dispersed in a hydrocarbon diluent. For example, in some embodiments, the preformed MgCl2 support comprising MgCl2 particles dispersed in a hydrocarbon diluent can be heat-treated at a temperature of 100°C or higher, 120°C or higher, 130°C or higher, 150°C or higher, or even 190°C or higher to produce the preformed MgCl2 support. In some embodiments, the MgCl2 slurry may be heat-treated at temperatures of 100°C to 500°C, 100°C to 300°C, 100°C to 200°C, 120°C to 500°C, 120°C to 300°C, 120°C to 200°C, 130°C to 500°C, 130°C to 300°C, 130°C to 200°C, 150°C to 500°C, 150°C to 300°C, 150°C to 200°C, 190°C to 500°C, or 190°C to 300°C to produce a heat-treated MgCl2 support. In some embodiments, the MgCl2 slurry may be heat-treated at two or more different temperatures during the heat treatment.

[0026] The preformed MgCl2 carrier can be heat-treated for 30 minutes (0.5 hours), 1 hour, 2 hours, 3 hours, 6 hours, or 10 hours to produce a heat-treated MgCl2 carrier. For example, in some embodiments, the preformed MgCl2 support may be heat-treated for 0.5 hours to 240 hours, 0.5 hours to 120 hours, 0.5 hours to 48 hours, 0.5 hours to 24 hours, 1 hour to 240 hours, 1 hour to 120 hours, 1 hour to 48 hours, 1 hour to 24 hours, 2 hours to 240 hours, 2 hours to 120 hours, 2 hours to 48 hours, 2 hours to 24 hours, 3 hours to 240 hours, 3 hours to 120 hours, 3 hours to 48 hours, 3 hours to 24 hours, 6 hours to 240 hours, 6 hours to 120 hours, 6 hours to 48 hours, 6 hours to 24 hours, 10 hours to 240 hours, 10 hours to 120 hours, 10 hours to 48 hours, or 10 hours to 24 hours to produce the heat-treated MgCl2 support. In some embodiments, when the heat treatment temperature is above 200°C, the treatment time may be reduced to less than 30 minutes or less than 10 minutes.

[0027] In some embodiments, heat-treating the preformed MgCl2 support may include agitating the MgCl2 slurry. Agitation of the MgCl2 slurry may be performed simultaneously with heat-treating the MgCl2 slurry at a temperature of at least 100°C for at least 30 minutes. In some embodiments, the MgCl2 slurry may be agitated at speeds up to 1000 rpm, up to 100 rpm, 1 rpm to 100 rpm, or 1 rpm to 100 rpm. In some embodiments, heat-treating the MgCl2 support may include heat-treating the MgCl2 in an inert atmosphere. "Inert atmosphere" refers to an atmosphere composed of compounds and / or gases that do not react with any other components of the MgCl2 support or the heterogeneous pre-catalyst. For example, heat-treating the MgCl2 support may be carried out in the presence of an inert gas, such as nitrogen or argon, that does not react with MgCl2.

[0028] In some embodiments, the heat-treated MgCl2 support may be a product of a heat-treated preformed MgCl2 support. The heat-treated MgCl2 support may comprise heat-treated MgCl2 particles dispersed in a hydrocarbon diluent. Without being bound by theory, it is believed that heat-treated MgCl2 supports can modify the surface morphology and surface area of ​​MgCl2 particles. The resulting alteration in the surface morphology and surface area of ​​MgCl2 due to heat treatment can modify the activity of the heterogeneous pre-catalyst for olefin polymerization, and alter the polymerization behavior of the heterogeneous pre-catalyst as well as the molecular weight and composition of the resulting polymer. In some embodiments, after heat treatment, the heat-treated MgCl2 support may have a 50m... 2 / g to 1000m2 / g、200m 2 / g to 1000m 2 / g, or 400m 2 / g to 1000m 2 The average surface area is approximately 400 m² / g. In some embodiments, the heat-treated MgCl₂ support may have an average surface area of ​​approximately 400 m² / g. 2 / g average surface area.

[0029] After preparing the preformed MgCl2 support, it can be brought into contact with a chlorinating agent. The chlorinating agent may have the structural formula A(Cl). x (R 1 ) 3-x Or Si(Cl) y (R 1 ) 4-y Where A is an element selected from the group consisting of: boron, aluminum, gallium, indium, and tellurium, and R... 1 For (C1-C 30 A is a hydrocarbon group, where x is 1, 2, or 3, and y is 1, 2, 3, or 4. In some embodiments, A may be aluminum. In some embodiments, the chlorinating agent may have the structural formula Al(Cl). x (R 1 ) 3-x Or structural formula Si(Cl) y (R 1 ) 4-y , where R 1 For (C1-C 30 The chlorinating agent is selected from aluminum trichloride, methylaluminum dichloride, dimethylaluminum chloride, ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum dichloride, diisobutylaluminum chloride, n-hexylaluminum dichloride, di-n-hexylaluminum chloride, n-octylaluminum dichloride, di-n-octylaluminum chloride, boron trichloride, phenylboron dichloride, dicyclohexylboron chloride, silicon tetrachloride, methyltrichlorosilane, dimethylchlorosilane, trichlorotrimethylsilane, ethyltrichlorosilane, dichlorodiethylsilane, and dichlorodiethylsilane. The chlorinating agent may be trichloroethylsilane, n-propyltrichlorosilane, dichlorodi(n-propyl)silane, trichlorotri(n-propyl)silane, isopropyltrichlorosilane, dichlorodiisopropylsilane, trichlorotriisopropylsilane, n-butyltrichlorosilane, dichlorodi(n-butyl)silane, trichlorotri(n-butyl)silane, isobutyltrichlorosilane, dichlorodiisobutylsilane, trichlorotriisobutylsilane, cyclopentyltrichlorosilane, dichlorodicyclopentylsilane, n-hexyltrichlorosilane, cyclohexyltrichlorosilane, dichlorodicyclohexylsilane, or combinations thereof. In some embodiments, the chlorinating agent may be selected from ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum dichloride, and diisobutylaluminum chloride.

[0030] The preformed MgCl2 support can be contacted with a chlorinating agent under conditions sufficient to adjust the preformed MgCl2 support. For example, the preformed MgCl2 support can be contacted with a chlorinating agent at temperatures of 0°C to 50°C, 0°C to 35°C, 25°C to 50°C, or 25°C to 35°C. The preformed MgCl2 support can be contacted with a chlorinating agent at these temperatures for 4 hours to 24 hours, 4 hours to 12 hours, 6 hours to 24 hours, or 6 hours to 12 hours. Without being bound by any theory, it is believed that adjusting the preformed MgCl2 support by contacting it with a chlorinating agent can promote or enhance the adsorption of additional metals, such as titanium, onto the preformed MgCl2 support. Including a chlorinating agent in the heterogeneous pre-catalyst can also convert any Ti and Mg compounds that are not chlorides into titanium chloride and MgCl2. The heterogeneous pre-catalyst may include a chlorinating agent sufficient to adjust the amount of MgCl2. In some embodiments, the amount of chlorinating agent that may be included in the heterogeneous pre-catalyst is less than the amount of excess chloride sufficient to chlorinate the metal-ligand complex donor compound. In some embodiments, the heterogeneous pre-catalyst may include a molar ratio of chlorinating agent to MgCl2 in a heterogeneous pre-catalyst of 0.05:1 to 2:1, 0.05:1 to 1:1, 0.05:1 to 0.5:1, 0.05:1 to 0.3:1, 0.07:1 to 2:1, 0.07:1 to 1:1, 0.07:1 to 0.5:1, 0.07:1 to 0.3:1, 0.1:1 to 2:1, 0.1:1 to 1:1, 0.1:1 to 0.5:1, or 0.1:1 to 0.3:1.

[0031] A pre-formed MgCl2 support conditioned by a chlorinating agent can be contacted with a titanium material. The titanium material can be any titanium compound or titanium complex that exhibits catalytic activity after activation with a co-catalyst and incorporation into the pre-catalyst. For example, in some embodiments, the titanium material may include titanium halides, titanium alkanols, or combinations thereof. In some embodiments, the titanium material is TiCl... 4-c (OR 3 ) c or TiCl 3-d (OR 3 ) d , where R 3 For (C1-C 20The titanium material may be a hydrocarbon group; c is 0, 1, 2, 3 or 4; and d is 0, 1, 2 or 3. For example, in some embodiments, the titanium material may include, but is not limited to, titanium tetrachloride (IV) (TiCl4), titanium trichloride (III) (TiCl3), titanium diethoxydichloride (IV) (TiCl2(OC2H5)2), titanium diisopropoxydichloride (IV) (TiCl2(Oi-C3H7)2), titanium dibutoxydichloride (IV) (TiCl2(On-C4H9)2), titanium diisobutoxydichloride (IV) (TiCl2(Oi-C4H9)2), titanium triisopropoxydichloride (IV) (TiCl(Oi-C3H7)3), titanium tributoxydichloride (IV) (TiCl(On-C4H9)3), titanium triisobutoxydichloride (IV) (TiCl(Oi-C4H9)3), titanium tetraisopropoxide (IV) (Ti(O i Pr)4, alternatively Ti(Oi-C3H7)4, titanium ethoxide (IV) (Ti(OC2H5)4), titanium n-butoxide (IV) (Ti(On-C4H9)4), titanium isobutoxide (IV) (Ti(Oi-C4H9)4), titanium 2-ethylhexanoate (IV) (Ti(OCH2CH(C2H5)(C4H9))4), dichlorobis(2,2,6,6-tetramethyl-3,5-heptanedionyl)titanium (IV), tris(2,2,6,6-tetramethyl-3,5-heptanedionyl)titanium (III), tetrachlorobis(tetrahydrofuran)titanium (IV), trichlorotris(tetrahydrofuran)titanium (III), methyl trichloride (IV) or combinations thereof. In some embodiments, the titanium material may be titanium tetrachloride (IV) or titanium tetraisopropoxide (IV) (Ti(Oi-C3H7)4). i Pr)4).

[0032] The chlorinated preformed MgCl2 support can be contacted with titanium material under slurry conditions sufficient to form at least a portion of the titanium material adsorbed onto the preformed MgCl2 support. For example, in some embodiments, the chlorinated preformed MgCl2 support can be contacted with titanium material at temperatures of 0°C to 50°C, 0°C to 35°C, 25°C to 50°C, or 25°C to 35°C. In some embodiments, the chlorinated preformed MgCl2 support can be contacted with titanium material at such temperatures for periods of 1 minute to 72 hours, 0.5 hours to 24 hours, 1 hour to 12 hours, 1 hour to 6 hours, 3 hours to 72 hours, 3 hours to 24 hours, 3 hours to 12 hours, 6 hours to 72 hours, 6 hours to 24 hours, or 6 hours to 12 hours. In some embodiments, the heterogeneous pre-catalyst may include a molar ratio of titanium to MgCl2 in a heterogeneous pre-catalyst of 0.005:1 to 0.25:1, 0.005:1 to 0.15:1, 0.005:1 to 0.07:1, 0.01:1 to 0.25:1, 0.01:1 to 0.15:1, 0.01:1 to 0.07:1, 0.05:1 to 0.25:1, 0.05:1 to 0.15:1, or 0.05:1 to 0.07:1.

[0033] The preparation of heterogeneous precatalysts may further include contacting a slurry comprising a pre-formed MgCl2 support, a chlorinating agent, and a titanium material with a donor compound to produce the heterogeneous precatalyst. An electron donor compound refers to an organic molecule containing a functional group capable of donating a pair of electrons to an electron acceptor (typically a metal atom). In some embodiments, the donor compound may be a metal-ligand complex. Without being bound by theory, it is believed that metal-ligand complexes (L...) n M(Y) m (XR 2 ) b It can act as an electron donor molecule by gaining one or more lone pairs of electrons from one or more heteroatoms in the complex. As previously mentioned, metal-ligand complexes can have the structural formula (L). n M(Y) m (XR 2 ) b Where: M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR 2 It is an anionic ligand, wherein X is a heteroatom or contains a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20The metal-ligand complex is a heteroalkyl group; n is 0 (zero), 1, or 2; m is 0, 1, 2, 3, or 4; and b is 1, 2, 3, 4, 5, or 6. The metal-ligand complex can generally be charge-neutral. In some embodiments, the metal-ligand complex is soluble in hydrocarbon solvents, such as hydrocarbon diluents discussed earlier herein. For example, in some embodiments, the metal-ligand complex is soluble in a hydrocarbon diluent used to produce a preformed MgCl2 support for MgCl2. Without being bound by any theory, it is believed that soluble hydrocarbon solvents in MgCl2 slurries result in better dispersion of the metal-ligand complex in the slurry and promote interaction between the metal-ligand complex on the MgCl2 surface and the titanium material.

[0034] In some embodiments, the metal cation M may be a transition metal cation, including lanthanides and actinides. For example, in some embodiments, M may be selected from cerium, chromium, cobalt, copper, iron, lanthanum, manganese, neodymium, nickel, niobium, samarium, scandium, tantalum, titanium, tungsten, vanadium, yttrium, zinc, or zirconium, or combinations thereof, in any oxidation state. Alternatively, in some embodiments, the metal cation M may be a main group metal cation. Main group metal cations refer to cations containing metals / metalloids from Groups 1, 2, and 13-16 of the IUPAC periodic table. For example, in some embodiments, the metal cation M may include, but is not limited to, calcium, magnesium, aluminum, gallium, indium, thallium, or tin, in any oxidation state. In some embodiments, M may be selected from vanadium, titanium, chromium, scandium, zirconium, niobium, magnesium, calcium, or combinations thereof.

[0035] In some embodiments, one or more L may be a neutral ligand. In some embodiments, one or more L may comprise a neutral ligand containing an oxygen-, nitrogen-, or phosphorus-containing compound, such as ammonia, nitriles, pyridine, amines, phosphine, or combinations thereof. Examples of neutral ligands may include, but are not limited to, ethers, ketones, esters, amines, pyridines, phosphine, phosphites, other neutral ligands, or combinations thereof. In some embodiments, one or more L may be an oxygen group (=O). In some embodiments, X may be oxygen. In some embodiments, X may be a carboxylate group (-OC(=O)-).

[0036] In some embodiments, the metal-ligand complex may be a metal alkoxide or a metal oxyalkoxide. In some embodiments, the metal-ligand complex may have the structural formula M(OR) 2 ) e Metal alkoxides, wherein M is a metal cation; e is 2, 3, 4, 5, or 6; and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ) heteroalkyl group or its halide derivative. In other embodiments, the metal ligand complex may be having the structural formula M(=O)(OR) 2 )f A metal oxyalkoxide, wherein M is a metal cation; f is 1, 2, 3 or 4; and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ) heteroalkyl groups or their halide derivatives. In some embodiments, the metal-ligand complex may include at least one of the following: vanadium triethanolate (V), vanadium tri-n-propanol oxide (V) (VO(O) n Pr)3), Vanadium tributanol oxide (V)(VO(O) n Bu)3), Vanadium triisopropanol oxide (V)(VO(O) i Pr)3), Tetraisopropanetitanium (IV)(Ti(O) i Pr)4), Titanium ethoxydichloride (IV), Titanium diisopropoxydichloride (IV), Titanium diisopropoxydichloride (IV), Titanium diisobutoxydichloride (IV), Titanium diisobutoxydichloride (IV), Titanium triisopropoxydichloride (IV), Titanium triisobutoxydichloride (IV), Titanium tetraisopropoxide (IV) (Ti(O) i Pr)4), titanium n-butoxide (IV), titanium isobutoxide (IV), titanium 2-ethylhexanoate (IV), niobium n-butoxide (V), tantalum n-butoxide (V), scandium isopropoxide (III), yttrium n-butoxide (III), lanthanum isopropoxide (III), samarium isopropoxide (III), molybdenum ethoxide (V), iron ethoxide (III), cerium isopropoxide (IV), aluminum isopropoxide, or combinations thereof.

[0037] In some embodiments, the metal-ligand complex may be a metal carboxylate or a metal oxycarboxylate. In some embodiments, the metal-ligand complex may have the structural formula M(OC(O)R 2 ) g Metal carboxylates, of which R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 The heteroalkyl group and g is 2, 3, 4, 5 or 6. In some embodiments, the metal-ligand complex may have the structural formula M(=O)(OC(O)R 2 ) h Metal oxycarboxylate, wherein R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20The complex may contain a heteroalkyl group, and h is 1, 2, 3, or 4. In some embodiments, the metal-ligand complex may include at least one of the following: titanium 2-ethylhexanoate (IV), vanadium acetate, vanadium stearate (IV), chromium 2-ethylhexanoate (III), manganese 2-ethylhexanoate (II), iron 2-ethylhexanoate, cobalt 2-ethylhexanoate (II), nickel naphthenate (II), nickel 2-ethylhexanoate (II), copper 2-ethylhexanoate (II), copper naphthenate (II), zinc 2-ethylhexanoate, neodymium 2-ethylhexanoate (III), neodymium neodecanoate (III), zirconium 2-ethylhexanoate (IV), magnesium 2-ethylhexanoate, calcium 2-ethylhexanoate (II), calcium naphthenate (II), or combinations thereof. Naphthenates refer to metal salts of naphthenic acids. Naphthenic acids are mixtures of cycloaliphatic carboxylic acids and may be derived from formula C n H 2(n-z) O2 represents n, where n is 5 to 30 and z is 0 to 4. Naphthenic acids can be isolated from crude oil.

[0038] In some embodiments, the donor compound, such as the previously described metal-ligand complex, may be combined with a slurry comprising a preformed MgCl2 support component dispersed in a hydrocarbon diluent, the titanium material, and a chlorinating agent after the titanium material is adsorbed onto a preformed MgCl2 support to produce a heterogeneous pre-catalyst. In some embodiments, the metal-ligand complex may be combined with the slurry of the preformed MgCl2 support, titanium material, and chlorinating agent, and mixed immediately before the addition of the co-catalyst and the polymerization reaction for a period of 0.5 to 10 minutes. In some embodiments, the metal-ligand complex may be combined with the slurry of the preformed MgCl2 support, titanium material, and chlorinating agent, and mixed for more than 10 minutes before the addition of the co-catalyst and the polymerization reaction. The heterogeneous precatalyst may have a molar ratio of metal-ligand complex (i.e. donor compound) to titanium material of 0.1:1 to 10:1, 0.5:1 to 5:1, 1:1 to 1:3, 1:1 to 1:2.5, 1:1 to 1:2, 1:1.5 to 1:3, 1:1.5 to 1:2.5, 1:1.5 to 1:2, or 1:2 to 1:3.

[0039] In some embodiments, the heterogeneous precatalyst may optionally comprise one or more second transition metals, wherein at least a portion of the second metal is adsorbed onto a preformed MgCl2 support to produce a multimetallic heterogeneous precatalyst. The second transition metal may be independently selected from zirconium, hafnium, vanadium, scandium, niobium, tantalum, chromium, molybdenum, and tungsten. In some embodiments, the second transition metal may be independently selected from zirconium, hafnium, vanadium, and chromium. These second transition metals may be incorporated into the heterogeneous precatalyst in any of a variety of ways known to those skilled in the art, but typically, for example in a liquid phase, such as in a suitable hydrocarbon diluent, contact between the preformed MgCl2 support comprising titanium material and one or more selected second transition metals may be suitable to ensure the deposition of one or more second transition metals to form a multimetallic heterogeneous precatalyst. In some embodiments, the second transition metal may be incorporated into the heterogeneous precatalyst prior to a metal-ligand complex.

[0040] Not wanting to be bound by theory, it is believed that in excess chlorinating agent Al(Cl) x (R 1 ) 3-x Or Si(Cl) y (R 1 ) 4-y Given its existence, it has the structural form (L). n M(Y) m (XR 2 ) b A portion of the metal-ligand complex can be chlorinated and lose its function as an electron donor. Therefore, in this case, the titanium substance is TiCl. 4-c (OR 3 ) c or TiCl 3-d (OR 3 ) d In some embodiments, the chlorinating agent (Al(Cl)) x (R 1 ) 3-x and / or Si(Cl) y (R 1 ) 4-y The total amount of Cl in the catalyst and the OR in the heterogeneous catalyst 3 and XR 2 The total amount (e.g., OR) 3 and XR 2 The molar ratio of the total (total) is 0.33 to 1.45, 0.40 to 1.14, or 0.50 to 0.94.

[0041] In some embodiments, when the metal-ligand complex is a metal alkoxide, metal oxyalkoxide, metal carboxylate, metal oxycarboxylate, or a halide derivative of these compounds, and the metal-ligand complex is identical to the Ti substance or the second transition metal, the metal-ligand complex may be added to a pre-forming catalyst containing the same Ti compound or the same second transition metal compound. For example, when Ti(O) i When Ti(O)4 is used as a Ti material in a pre-formed heterogeneous pre-catalyst and also as a metal-ligand complex, Ti(O) i Pr)4 can be added as a metal-ligand complex donor when using Ti(O) i Pr)4 is used as a pre-formed heterogeneous pre-catalyst in the production of Ti materials. In another embodiment, when VO(O) n When Pr)3 is used as a second transition metal and a metal-ligand complex, VO(O) n Pr)3 can be added as a metal-ligand complex donor to the use of VO(O) n Pr)3 is used as a second transition metal in the pre-formed heterogeneous pre-catalyst.

[0042] As previously discussed, in some embodiments, the heterogeneous precatalyst may include a pre-shaped heterogeneous precatalyst and a metal-ligand complex. As used herein, the term "pre-shaped heterogeneous precatalyst" refers to an existing functional Ziegler-Natta precatalyst composition that has been identified as having catalytic activity for polymerization and copolymerization reactions and becomes active when combined with a cocatalyst. In some embodiments, the pre-shaped heterogeneous precatalyst may include at least a titanium material and a MgCl2 support. For example, in some embodiments, the titanium material may be titanium tetrachloride (TiCl4), such that the pre-shaped heterogeneous precatalyst comprises TiCl4 and a MgCl2 support. In some embodiments, the titanium material may be titanium tetraisopropoxide (Ti(O) i Pr)4), so that the pre-formed heterogeneous pre-catalyst includes Ti(O) i Pr)4 and MgCl2 supports. It should be understood that Ti(O) i At least a portion of Pr)4 can be converted into one or more Ti chlorides after chlorination with a chlorinating agent. In some embodiments, the preformed heterogeneous precatalyst may include any commercially available Ziegler-Natta precatalyst comprising at least TiCl4 and MgCl2 supports and becoming active when combined with a cocatalyst.

[0043] Heterogeneous precatalysts can be prepared by contacting a metal-ligand complex with a pre-formed heterogeneous precatalyst. For example, in some embodiments, methods for preparing the heterogeneous precatalyst may include providing a pre-formed heterogeneous precatalyst comprising a titanium material and a MgCl2 support. The method may further include contacting the pre-formed heterogeneous precatalyst with a metal-ligand complex without additional chlorination. Not to be bound by theory, it is believed that additional chlorination can convert the metal-ligand complex into one or more chloride compounds, thereby weakening its role as an electron donor.

[0044] In some embodiments, the heterogeneous precatalyst may include a pre-shaped heterogeneous precatalyst and a metal-ligand complex, wherein the pre-shaped heterogeneous precatalyst comprises a titanium material (such as titanium tetrachloride) and a MgCl2 support. In these embodiments, adding the metal-ligand complex to the pre-shaped heterogeneous precatalyst can modify the pre-shaped heterogeneous precatalyst to produce the heterogeneous precatalyst of this disclosure, which is capable of producing ethylene-based polymers with larger Mw and higher density fractions and reduced comonomer weight percentages. Contact between the pre-shaped heterogeneous precatalyst and the metal-ligand complex can occur under a wide variety of conditions. Such conditions may include, for example, contacting the pre-shaped heterogeneous precatalyst with the metal-ligand complex at temperatures of 0°C to 100°C, 0°C to 80°C, 15°C to 80°C, 15°C to 60°C, 15°C to 50°C, or 20°C to 50°C in an inert atmosphere (such as nitrogen, argon, or other inert gases). After contact, it is not necessary to separate the hydrocarbon-soluble components from the hydrocarbon-insoluble components. Before contacting the co-catalyst to form the catalyst system, the contact time between the pre-formed heterogeneous catalyst and the metal-ligand complex can be greater than or equal to 10 minutes, greater than or equal to 0.5 hours, greater than or equal to 1 hour, greater than or equal to 24 hours, greater than or equal to 168 hours, or greater than or equal to 700 hours. It is believed that the effect of the metal-ligand complex may change slightly or moderately with aging. However, these effects still persist for a considerable period. The molar ratio of the metal-ligand complex (i.e., the donor compound) to the titanium material in the pre-formed heterogeneous catalyst can be 0.1:1 to 10:1, 0.5:1 to 5:1, 1:1 to 1:3, 1:1 to 1:2.5, 1:1 to 1:2, 1:1.5 to 1:3, 1:1.5 to 1:2.5, 1:1.5 to 1:2, or 1:2 to 1:3.

[0045] The heterogeneous pre-catalyst can be activated by contacting it with a co-catalyst. The co-catalyst may include at least one organometallic compound, such as alkylaluminum or haloalkylaluminum, aluminoxane, alkanol alkylaluminum, haloalkylaluminum, Grignard reagent, alkali metal aluminum hydride, alkyl metal, alkali metal borohydride, alkali metal hydride, alkaline earth metal hydride, etc. In some embodiments, the co-catalyst may be an organoaluminum compound. In some embodiments, the co-catalyst may be selected from alkylaluminum, haloalkylaluminum, haloalkylaluminum, and mixtures thereof. In some embodiments, the co-catalyst may be selected from triethylaluminum, trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), diethylaluminum ethanol, and mixtures thereof. As previously discussed, the catalyst system may include a heterogeneous pre-catalyst and a co-catalyst. Preparing the catalyst system may include contacting the heterogeneous pre-catalyst with the co-catalyst.

[0046] The formation of a catalyst system from a heterogeneous pre-catalyst and a co-catalyst can take place either just before entering the polymerization reactor or in situ (at an appropriate location) before polymerization. Therefore, the contact between the heterogeneous pre-catalyst and the co-catalyst (or a pre-formed heterogeneous pre-catalyst, metal-ligand complex, and co-catalyst) can occur under a wide variety of conditions to prepare the catalyst system. Such conditions may include, for example, contacting the heterogeneous pre-catalyst and co-catalyst under an inert atmosphere (such as nitrogen, argon, or other inert gases) at temperatures ranging from 0°C to 250°C, 0°C to 200°C, 15°C to 250°C, 15°C to 200°C, 15°C to 50°C, or 150°C to 250°C. In the preparation of the catalytic reaction products (i.e., the catalyst system), it is not necessary to separate the hydrocarbon-soluble components from the hydrocarbon-insoluble components. Prior to the polymerization reaction, the contact time between the heterogeneous pre-catalyst and the co-catalyst can be greater than 0 minutes to 10 days, greater than 0 minutes to 60 minutes, greater than 0 minutes to 5 minutes, 0.1 minutes to 5 minutes, 0.1 minutes to 2 minutes, or 1 minute to 24 hours. Various combinations of these conditions can be used. In some embodiments, the catalyst system may have a molar ratio of co-catalyst to titanium material in the heterogeneous pre-catalyst of 0.5:1 to 50:1, 3:1 to 20:1, 3:1 to 15:1, 3:1 to 10:1, 3:1 to 8:1, 5:1 to 20:1, 5:1 to 15:1, 5:1 to 10:1, 8:1 to 20:1, or 8:1 to 15:1.

[0047] In some embodiments, the metal-ligand complex may be used as an external donor compound rather than incorporated into the heterogeneous pre-catalyst. For example, in some embodiments, the catalyst system may include a pre-formed heterogeneous pre-catalyst, a metal-ligand complex, and a co-catalyst as previously described herein. The catalyst system may be prepared by contacting the pre-formed heterogeneous pre-catalyst, the metal-ligand complex, and the co-catalyst. For example, when the metal-ligand complex is used as an external donor compound, the metal-ligand complex may be combined with the pre-formed heterogeneous pre-catalyst and the co-catalyst immediately before introducing the catalyst system into the polymerization reactor system. In some embodiments, the pre-formed heterogeneous pre-catalyst, the metal-ligand complex, and the co-catalyst as previously described herein may be added to the reactor simultaneously and separately. In these embodiments, the contact between the pre-formed heterogeneous pre-catalyst and the metal-ligand complex is carried out in the polymerization reactor.

[0048] Once a catalyst system comprising a heterogeneous pre-catalyst and a co-catalyst has been prepared, the catalyst system can be used in polymerization or copolymerization methods for polymerizing olefins. For example, in some embodiments, the catalyst system can be used in polymerization or copolymerization methods to produce ethylene-based polymers, such as linear low-density polyethylene (LLDPE) and other ethylene-based polymers. In some embodiments, the polymerization or copolymerization method may include contacting ethylene and optionally one or more α-olefin comonomers with a catalyst system comprising a heterogeneous pre-catalyst and optionally a co-catalyst to form an ethylene-based polymer. The olefin polymerization / copolymerization reaction may be carried out in a reaction medium. The reaction medium may be a hydrocarbon diluent, such as isoparaffins, aliphatic hydrocarbons, or any of the other hydrocarbon diluents previously described in this disclosure. The olefin polymerization / copolymerization method may include contacting an olefin or combination of olefins with a reaction medium in the presence of a catalyst system comprising a heterogeneous pre-catalyst, or a pre-formed heterogeneous pre-catalyst and a metal-ligand complex and a co-catalyst. Conditions may be any suitable conditions, and a molecular weight modifier, such as hydrogen, may also be present in the reaction vessel to suppress the formation of undesirable high molecular weight polymers.

[0049] In the presence of the catalyst system disclosed herein, any ethylene polymerization or copolymerization reaction system can be used to produce ethylene-based polymers. Such ethylene polymerization or copolymerization reaction systems may include, but are not limited to, slurry-phase polymerization methods, solution-phase polymerization methods, gas-phase polymerization methods, and combinations thereof. The polymerization or copolymerization method can be carried out in one or more conventional reactors, examples of which include, but are not limited to, loop reactors, stirred tank reactors, fluidized bed reactors, batch reactors in parallel or series, and / or any combination thereof. In some embodiments, the polymerization method can be carried out in two or more reactors in series, in parallel, or in combination thereof. In other embodiments, the polymerization method can be carried out in a single reactor. The polymerization method can be a batch polymerization method or a continuous polymerization method. For example, in some embodiments, the polymerization method can be a batch polymerization method, which can be carried out in a stirred tank reactor. In some embodiments, the polymerization method can be a continuous polymerization reaction, such as a polymerization reaction carried out in a continuous solution polymerization reactor. In some embodiments, the polymerization method can be carried out in two continuous solution polymerization reactors in series, and one or more molecular catalysts can be charged into the first reactor, and the catalyst system disclosed herein can be charged into the second reactor. In some embodiments, the polymerization method may be performed in two continuous solution polymerization reactors in series, and the catalyst system disclosed herein may be used in the first reactor, and one or more metallocene or molecular catalysts may be used in the second reactor. In some embodiments, the polymerization method may include a reactor in which the catalyst system disclosed herein and another polymerization catalyst system are present. The other catalyst system may include any Ziegler-Natta catalyst and any molecular catalyst. The molecular catalyst is a polymerization catalyst system that contains a transition metal complex pre-catalyst having a well-defined molecular structure, such as a metallocene. In other embodiments, the polymerization method may include two or more polymerization steps. In these embodiments, a catalyst system containing a heterogeneous pre-catalyst disclosed herein may be used in any one or more polymerization steps.

[0050] Polymers produced by polymerization / copolymerization methods utilizing the catalyst system disclosed herein can be C2-C 20 Homopolymers of α-olefins, such as ethylene, propylene, or 4-methyl-1-pentene. In some embodiments, the polymer produced in the presence of a heterogeneous pre-catalyst may comprise copolymers of ethylene or propylene with at least one or more α-olefin comonomers. In some embodiments, the polymer may be an ethylene-based polymer, such as ethylene with the above C3-C... 20A copolymer of at least one of α-olefins and other unsaturated comonomers. In some embodiments, the comonomer may be an α-olefin comonomer having no more than 20 carbon atoms. For example, in some embodiments, the α-olefin comonomer may have 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers may include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. In some embodiments, the ethylene-based polymer may include an α-olefin comonomer selected from the group consisting of 1-butene, 1-hexene, and 1-octene. In some embodiments, the ethylene-based polymer produced in the presence of the catalyst system disclosed herein may be a copolymer of ethylene monomer units and comonomer units selected from 1-butene, 1-hexene, 1-octene, or combinations thereof.

[0051] In polymerization / copolymerization methods utilizing the catalyst system described herein, polymerization is achieved by adding a catalytic amount of the catalyst system to a polymerization reactor containing a selected α-olefin monomer (e.g., ethylene and / or one or more α-olefin comonomers), or vice versa. The polymerization reactor can be maintained at a temperature of 50°C to 300°C. For example, in some embodiments, the polymerization reactor can be maintained at temperatures of 50°C to 230°C, 50°C to 200°C, 100°C to 300°C, 100°C to 230°C, 100°C to 200°C, or 60°C to 120°C. In some non-limiting embodiments, the residence time of the reactants, the catalyst system, or both in the polymerization reactor can be 5 minutes to 4 hours, 5 minutes to 20 minutes, or 0.5 hours to 4 hours. Alternatively, longer or shorter residence times can be used. It is generally desirable to carry out polymerization in the absence of moisture and oxygen and in the presence of the catalyst system. The amount of catalyst in the system should be sufficient to provide the desired productivity (e.g., yield) of the ethylene-based polymer, but not so large that the amount of catalyst in the system becomes prohibitively expensive. However, it should be understood that the most favorable catalyst concentration will depend on the polymerization conditions, such as temperature, pressure, solvent, and the presence of catalyst poisons.

[0052] In some embodiments, the polymerization / copolymerization process may be carried out at relatively low pressures, such as 150 to 3,000 psig (1.0 to 20.7 MPa), 250 to 1,000 psig (1.7 to 6.9 MPa), or 450 to 800 psig (3.1 to 5.5 MPa). However, polymerization / copolymerization in the presence of the catalyst system described herein may be carried out at pressures ranging from atmospheric pressure to pressures determined by the capacity of the polymerization equipment (e.g., pressure ratings).

[0053] In some embodiments, the polymerization / copolymerization method may include a support, which may be an inert organic diluent, excess monomer, or both. Supersaturation of the support and polymer is generally avoided during the polymerization / copolymerization method. If such saturation of the support and polymer occurs before the catalyst system is exhausted, then the full efficiency of the catalyst system may not be achieved. In some embodiments, the polymerization / copolymerization method may be operated under conditions sufficient to maintain the amount of polymer in the support / diluent at a concentration less than the supersaturation concentration of the polymer. For example, in some embodiments, the polymerization / copolymerization method may be operated under conditions sufficient to maintain the amount of polymer in the support / diluent at less than 30 weight percent (wt%) based on the total weight of the reaction mixture. In some embodiments, the polymerization / copolymerization method may include mixing or stirring the reaction mixture to maintain temperature control and enhance the homogeneity of the polymerization reaction throughout the polymerization region. In some embodiments, such as when a faster reaction is carried out with a relatively active catalyst, if a diluent is included, the polymerization / copolymerization method may include reflux of the monomer and diluent to remove at least some of the heat of reaction. In some embodiments, heat transfer devices (e.g., heat exchangers, cooling jackets, or other heat transfer components) may be provided to remove at least a portion of the exothermic reaction of the polymerization.

[0054] In some embodiments, the reaction mixture added to the polymerization / copolymerization process may include an amount of ethylene monomer sufficient to maintain reactor stability and increase catalyst efficiency. In some embodiments, the reaction mixture may have a molar ratio of diluent to ethylene monomer of 1:2 to 1:8, 1:2 to 1:5, 1:3 to 1:8, or 1:3 to 1:5. In some embodiments, a portion of excess ethylene monomer may be discharged from the polymerization process to maintain the concentration of ethylene monomer in the reactor.

[0055] In some embodiments, the polymerization / copolymerization method may include contacting the reaction mixture with hydrogen during the reaction. The hydrogen may be operable to reduce the molecular weight of the ethylene-based polymer and to reduce the formation of ultra-high molecular weight molecules in the ethylene-based polymer. In some embodiments, the concentration of hydrogen in the reaction mixture may be maintained at 0.001 mol to 1 mol per mole of monomer, wherein the monomer includes ethylene monomer and any optional α-olefin comonomer. Hydrogen may be added to the polymerization reactor along with the monomer stream, as a separate hydrogen feed stream, or both. Hydrogen may be added to the polymerization reactor before, during, and / or after the monomer is added to the polymerization reactor. In some embodiments, hydrogen may be added before or during the addition of a catalyst system. In some embodiments, the polymerization / copolymerization method may be carried out without introducing hydrogen.

[0056] The resulting ethylene-based polymer can be recovered from the polymerization mixture by removing unreacted monomers, comonomers, diluents, or both. In some embodiments, additional impurity removal may not be necessary. The resulting ethylene-based polymer may contain small amounts of catalyst residue. The resulting ethylene-based polymer may be further melt-screened. For example, the ethylene-based polymer can be melt-spun using an extruder and then passed through one or more activated sieves positioned in a series of more than one, wherein each activated sieve has a micron retention size of approximately 2 μm to 400 μm. During melt screening, the mass throughput of the ethylene-based polymer can be 5 psi / h / inch. 2 Approximately 100 lbs / hour / inch 2 .

[0057] Compared to comparative polymers produced using a pre-catalyst that does not include a metal-ligand complex donor compound but is otherwise identical, ethylene-based polymers produced using the catalyst system disclosed herein exhibit increased molecular weight (Mw), increased high-density precipitate (HDF), and a decreased weight percentage of α-olefin comonomers. The increased molecular weight capability of the heterogeneous pre-catalyst and catalyst system disclosed herein allows polymerization / copolymerization processes to be carried out at higher process temperatures. This enables the production of ethylene-based polymers at higher throughput rates and exhibits improved properties, such as optical properties and / or dart / impact balance, compared to polymers produced at lower process temperatures. Furthermore, the catalyst system disclosed herein can be used in conjunction with molecular catalyst systems to produce bimodal polymers, wherein the catalyst system disclosed herein produces polymer components with high molecular weight and low comonomer content.

[0058] Ethylene-based polymers may include less than 50 wt% of units derived from one or more α-olefin comonomers. All individual values ​​and subranges of less than 50 wt% are included and disclosed herein. For example, in some embodiments, ethylene-based polymers may include less than or equal to 30 wt%, less than or equal to 20 wt%, less than or equal to 15 wt%, less than or equal to 10 wt%, less than or equal to 8 wt%, less than or equal to 5 wt%, or less than or equal to 3 wt% of units derived from one or more α-olefin comonomers. Ethylene-based polymers may include at least 50 wt% of units derived from ethylene. All individual values ​​and subranges from at least 50 wt% to 100 wt% are included and disclosed herein. For example, in some embodiments, the ethylene-based polymer may contain 70 wt% to 100 wt%, 80 wt% to 100 wt%, 85 wt% to 100 wt%, 90 wt% to 100 wt%, 95 wt% to 100 wt%, or even 97 wt% to 100 wt% of ethylene-derived units.

[0059] Ethylene-based polymers produced in the presence of the catalyst system disclosed herein may additionally include additional components, such as other polymers and / or additives. Examples of additives may include, but are not limited to, antistatic agents, colorants, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. In some embodiments, antioxidants, such as IRGAFOS, available from Ciba Geigy, may be used. TM 168 and IRGANOX TM 1010 can be used to protect ethylene-based polymer compositions from thermal and / or oxidative degradation. The ethylene-based polymer may contain any amount of additives. For example, in some embodiments, the ethylene-based polymer may include 0.0 wt% to 10.0 wt%, 0.0 wt% to 7.0 wt%, 0.0 wt% to 5.0 wt%, 0.0 wt% to 3.0 wt%, 0.0 wt% to 2.0 wt%, 0.0 wt% to 1.0 wt%, or even 0.0 wt% to 0.5 wt% of additives based on the total weight of the ethylene-based polymer composition including such additives.

[0060] Ethylene-based polymers produced in the presence of the catalyst systems disclosed herein can include a wide variety of products, including LLDPE in specific embodiments, but also high-density polyethylene (HDPE), plastomers, medium-density polyethylene, and polypropylene copolymers. For these and other applications, articles exhibiting an overall increase in quality can be prepared due to the increase in the average molecular weight and high-density fraction of the ethylene-based polymer. Useful molding operations for the polymers can include, but are not limited to, extrusion and co-extrusion of films, sheets, tubes, and fibers, as well as blow molding, injection molding, and rotational molding. Films can include blow-molded or cast films formed by co-extrusion or by lamination, and said films can be used as, for example, shrink films, cling films, stretch films, sealing films, oriented films, snack packaging, heavy-duty bags, grocery bags, baked and frozen food packaging, medical packaging, industrial liners, agricultural film applications, and diaphragms in food contact and non-food contact applications. Fibers can include melt spinning, solution spinning, and meltblown fiber operations for use in woven or nonwoven forms in the manufacture of filter paper, diaper fabrics, medical clothing, and geotextiles. Extruded products may include medical catheters, wire and cable coatings, geomembranes, and pond liners. Molded products may include single-layer and multi-layer constructions in the form of bottles, cans, large hollow products, rigid food containers, and toys.

[0061] Test methods

[0062] Specific surface area

[0063] The specific surface area of ​​the MgCl2 support was measured using the Brunauer Emmett Teller (BET) surface area method. A Micromeritics Tristar 3020 surface area analyzer was used. 30 mL of MgCl2 slurry was filtered to remove the solvent and then re-slurryed in 30 mL of hexane. The resulting slurry was filtered again under an inert atmosphere and washed with additional hexane. This process was repeated once to obtain a MgCl2 filter cake. Residual solvent was removed from the filter cake under vacuum. The filter cake was further dried by loading 0.2 g of vacuum-dried MgCl2 sample into the tube under an inert atmosphere using a Micromeritics Vac Prep 061 with a 0.5-inch (1.27 cm) sample tube and a Transeal stopper designed for inert sample protection. The sample tube was connected to the Vac Prep 061 unit under nitrogen purging. The sample tube was vacuum-treated by opening the Transeal stopper and placed in a heating block with an aluminum tube protector. The sample was dried under vacuum at 110°C for 3 hours on a Vac Prep 061 unit. Nitrogen gas was then introduced into the sample tube. The dried sample was allowed to cool to room temperature, and then the sample tube was disconnected from the Vac Prep 061 unit to obtain a completely dried sample. Under an inert atmosphere, 0.1500 to 0.2000 g of the completely dried sample was transferred to a clean sample tube with a tube-filling rod. The sample tube was then sealed with a Transeal stopper and connected to a Tristar 3020 instrument for surface area measurement. The QUICKSTART method was used to acquire the data.

[0064] density

[0065] Density is measured according to ASTM D792 and is expressed in grams per cubic centimeter (g / cc or g / cm³). 3 Report as a unit.

[0066] Melt Flow Index

[0067] Melt flow index (I2) is measured according to ASTM D1238 at 190°C and a 2.16 kg load. The melt flow index (I2) is obtained using a CEAST7026 or Instron MF20 instrument. The instrument conforms to ASTM D1238, Methods E and N. The melt flow index (I2) is reported as grams eluted per 10 minutes (g / 10 min). The melt flow index I2 is used for polymer characterization. Higher I2 values ​​are generally associated with lower Mw.

[0068] Gel permeation chromatography (GPC)

[0069] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) connected to a Precision Detector (now Agilent Technologies) 2-angle laser scattering (LS) detector 2040. A 15-degree angle was used for all light scattering measurements. The autosampler chamber was set to 160°C, and the column chamber to 150°C. Three Agilent “Mixed B” 30cm 20µm linear mixed-bed columns were used. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was bubbled with nitrogen. The injection volume was 200 μL, and the flow rate was 1.0 mL / min.

[0070] The GPC column assembly was calibrated using at least 20 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 to 8,400,000, arranged in a mixture of six “mixtures” with individual molecular weights spaced at least ten times apart. The standards were purchased from Agilent Technologies. For polystyrene standards with molecular weights equal to or greater than 1,000,000, 0.025 g was prepared in 50 mL of solvent, and for those with molecular weights less than 1,000,000, 0.05 g was prepared in 50 mL of solvent. The polystyrene standards were dissolved by gentle stirring at 80°C for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (EQU.1) (as described in Williams and Ward, *Journal of Polymer Science: Polymer Letters*, 6, 621 (1968)).

[0071] M 聚乙烯 =A×(M) 聚苯乙烯 ) B EQU.1

[0072] Where M is the molecular weight, A has a value of 0.4315 and B equals 1.0.

[0073] A fifth-order polynomial was used to fit the corresponding polyethylene equivalent calibration point. Small adjustments were made to A (from approximately 0.415 to 0.44) to correct for column resolution and band broadening effects, resulting in the NIST standard NBS1475 at 52,000 Mw.

[0074] Total plate counts were performed on the GPC column assembly using eicosane (prepared in 50 mL of TCB at 0.04 g and dissolved under gentle stirring for 20 min). Plate counts (Equation 2 (EQU.2)) and symmetry (Equation 3 (EUQ.3)) were measured on a 200 μL injection according to the following equations:

[0075]

[0076] Where RV is the retention volume in milliliters, peak width is in milliliters, peak value is the maximum height of the peak, and 1 / 2 height is half the height of the peak value.

[0077]

[0078] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the position of the maximum peak, one-tenth height is 1 / 10 of the height of the peak maximum, and the term "following peak" refers to the tail of the peak at a slightly later retention volume compared to the peak maximum, and the term "forward peak" refers to the front of the peak at a slightly earlier retention volume compared to the peak maximum. The plate count of the chromatographic system should be greater than 24,000, and the symmetry should be between 0.98 and 1.22.

[0079] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, with a target sample concentration of 2 mg / ml. Solvent (containing 200 ppm BHT) was added to a pre-nitrogen-bubbled vial covered with a septum via a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for 2 hours with "low-speed" oscillation.

[0080] Mn (GPC) Mw (GPC) and Mz (GPC) The calculation is based on using PolymerChar GPCOne TM The software uses the GPC results from the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, the baseline-subtracted IR chromatograph at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) in Equation 1, based on Equations 4-6 (EQU.4, EQU.5, and EQU.6).

[0081]

[0082] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (nominal flow rate) for each sample by comparing the RV (RV(FM sample)) of the corresponding decane peak within the sample with the RV (RV(FM calibrated)) of the decane peak within the narrow standard calibration. It was then assumed that any change in the decane marker peak time was related to a linear shift in the flow rate (effective flow rate) over the entire run. To facilitate the highest accuracy in RV measurement of the flow marker peak, a least-squares fitting procedure was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The true peak position was then solved using the first derivative of the quadratic equation. After calibration based on the flow marker peak, the effective flow rate (relative to narrow standard calibration) was calculated according to Equation 7 (EQU.7). Via PolymerChar GPCOne TM The software processes the peak values ​​of the flow markers. Acceptable flow rate correction ensures that the effective flow rate is within + / - 2% of the nominal flow rate.

[0083]

[0084] Using known short chain branch (SCB) frequencies (via 13 At least ten ethylene-based polymer standards (polyethylene homopolymers and ethylene / octene copolymers) measured by the C10 NMR method were calibrated using IR5 detector quantification, ranging from homopolymers (0 SCB / 1000 total C) to approximately 50 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branches. The weight-average molecular weight (Mw) of each standard ranged from 36,000 g / mol to 126,000 g / mol as determined by GPC-LALLS. The molecular weight distribution (Mw / Mn) of each standard ranged from 2.0 to 2.5 as determined by GPC. Example polymer properties of the copolymer standards are shown in Table A.

[0085] Table A: Copolymer Standards

[0086] Wt% comonomer IR5 area ratio SCB / 1000 total C Mw Mw / Mn 23.1 0.2411 28.9 37,300 2.22 14.0 0.2152 17.5 36,000 2.19 0.0 0.1809 0.0 38,400 2.20 35.9 0.2708 44.9 42,200 2.18 5.4 0.1959 6.8 37,400 2.16 8.6 0.2043 10.8 36,800 2.20 39.2 0.2770 49.0 125,600 2.22 1.1 0.1810 1.4 107,000 2.09 14.3 0.2161 17.9 103,600 2.20 9.4 0.2031 11.8 103,200 2.26

[0087] For each of the "copolymer" standards, calculate the "IR5 area ratio" (or "IR5" of the "area response of the IR5 methyl channel sensor minus the baseline" to the "area response of the IR5 measurement channel sensor minus the baseline"). 甲基通道面积 / IR5 测量通道面积(e.g., standard filters and filter wheels supplied by PolymerChar: part number IR5_FWM01 includes components as part of the GPC-IR instrument). A linear fit of the Wt% comonomer frequency to the “IR5 area ratio” is constructed in the form of Equation 8 (EQU.8):

[0088]

[0089] If there is significant spectral overlap between the molecular weight determined at each chromatogram slice and the end-capped (methyl) comonomer, then the wt% comonomer data can be corrected for end groups via the decapping mechanism.

[0090] Measurement of high-density fraction (HDF)

[0091] Improved comonomer content distribution (iCCD) analysis was performed using a crystallization elution fractionation (CEF) instrument (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and a Model 2040 two-angle light scattering detector (precision detector, currently Agilent Technologies). A 10cm (length) × 1 / 4" (ID) (0.635cm ID) stainless steel guard column filled with 20-27 micron glass (MoSCi Corporation, USA) was installed just before the IR-5 detector in the detector furnace. o-Dichlorobenzene (ODCB, 99% anhydrous or industrial grade) was used. Results were obtained from EMD. Chemicals silica gel 40 (particle size 0.2-0.5 mm, catalog number 10181-3) (previously used for drying ODCB solvent). The CEF instrument is equipped with an autosampler with N2 purging capability. ODCB is bubbled with dry nitrogen (N2) for one hour before use. Sample preparation is performed at 160°C with shaking at 4 mg / ml (unless otherwise specified) using the autosampler for 1 hour. The injection volume is 300 μL. The iCCD temperature profile is as follows: crystallization from 105°C to 30°C at 3°C / min, thermal equilibration at 30°C for 2 minutes (including elution time for soluble fractions set to 2 minutes), and elution from 30°C to 140°C at 3°C / min. The flow rate during crystallization is 0.0 mL / min. The flow rate during elution is 0.50 mL / min. Data is collected at one data point / second.

[0092] The iCCD column was filled with gold-plated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co.) in a 15cm (length) × 1 / 4" (ID) (0.635cm) stainless steel tube. The column was filled and conditioned using a slurry method, according to references (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO2017 / 040127A1). The final pressure using TCB slurry was 150 bar.

[0093] Column temperature calibration was performed using a mixture of reference material linear homopolymer polyethylene (comonomer content of zero, melt index (I2) of 1.0, polydispersity Mw / Mn of approximately 2.6 by conventional gel permeation chromatography, 1.0 mg / mL) and eicosane (2 mg / mL) in the ODCB. The iCCD temperature calibration consisted of the following four steps: (1) calculating the delay volume defined as the measured eicosane peak elution temperature minus the temperature offset within 30.00 °C; (2) subtracting the temperature offset of the elution temperature from the raw iCCD temperature data. It should be noted that this temperature offset is a function of experimental conditions, such as elution temperature, elution flow rate, etc.; (3) A linear calibration line for the conversion elution temperature is generated in the range of 30.00 °C and 140.00 °C, such that the linear homopolymer polyethylene reference has a peak temperature of 101.0 °C and the eicosane has a peak temperature of 30.0 °C; (4) For the soluble fraction measured isothermally at 30 °C, the elution temperature below 30.0 °C is linearly extrapolated according to the reference (Cerk and Cong et al., US9,688,795) by using an elution heating rate of 3 °C / min.

[0094] The relationship between comonomer content and elution temperature of iCCD was constructed using 12 reference materials (ethylene homopolymers and ethylene-octene random copolymers prepared with unit-point metallocene catalysts, with ethylene equivalent weight-average molecular weights ranging from 35,000 to 128,000). All these reference materials were analyzed in the same manner as previously specified at 4 mg / mL. The reported elution peak temperature was modeled as a function of octene mol% using linear regression, yielding Equation 9 (EQU.9) with an R² of 0.978.

[0095] (Elution temperature) = -6.3515 (octene mol%) + 101.000 EQU.9

[0096] For the entire resin, an integration window is set to integrate all chromatograms within the elution temperature range (calibrated to the specified temperatures) from 23.0°C to 115°C. The weight percentage of the high-density fraction (HDF) of the resin is defined by the following Equation 10 (EQU.10):

[0097]

[0098] Catalyst efficiency

[0099] Catalyst efficiency (“Eff”) is calculated based on the amount of ethylene consumed during polymerization divided by the number of grams of Ti used in the pre-homogeneous catalyst (ethylene(g) / Ti(g)). The number of grams of Ti refers to the number of grams of Ti contributed by the titanium material and excludes any Ti contributed by the electron donor compound (metal-ligand complex).

[0100] Example

[0101] Embodiments of this disclosure will be further illustrated by the following examples. It should be understood that the following examples are intended to be illustrative in nature and do not limit the scope of the foregoing disclosure or the appended claims.

[0102] Example A: Preparation of pre-formed catalyst compositions of Examples 1-12 and Comparative Examples 1-3.

[0103] In Example A, a pre-formed catalyst composition slurry comprising magnesium chloride, a chlorinating agent, and titanium was prepared for use in Examples 1-12 and Comparative Examples 1-3. (This information is from an ISOPAR (Information Technology and Research Center) of ExxonMobil Corporation.) TM In an isoparaffin solvent, a 20 wt% heptane solution of n-butylethyl magnesium was diluted to a concentration of 0.20 M as an inert hydrocarbon diluent. Hydrochloric acid (HCl) was slowly added to the 0.2 M n-butylethyl magnesium solution with stirring at 30 °C until the Cl / Mg molar ratio reached 2.04 (mol Cl / mol Mg). Throughout the reaction, the temperature of the reaction mixture was maintained at 30 °C ± 3 °C. A magnesium chloride (MgCl2) slurry was obtained without separating the solid MgCl2 from the liquid diluent.

[0104] A 15% heptane solution of ethylaluminum dichloride (EADC) was slowly added to a MgCl2 slurry at 30°C with stirring until the EADC / Mg molar ratio reached 0.3 (mol EADC / mol Mg). The temperature of the reaction mixture was maintained at 30°C ± 3°C during the addition. The mixture was then aged at 30°C for 4 hours.

[0105] Subsequently, a 51% heptane solution of titanium isopropoxide (IV) was slowly added to the mixture at 30°C with stirring until the Ti / Mg molar ratio reached 0.075 (mol Ti / mol Mg). During the addition, the temperature of the reaction mixture was maintained at 30°C ± 3°C. The mixture was then allowed to age again at 30°C for at least 8 hours. ISOPAR was used. TM The concentration of the catalyst formulation before adjusting with E-chain alkane solvent. The final Ti concentration of the pre-formed catalyst composition in the hydrocarbon diluent of Example A is 0.12 M. The pre-formed catalyst composition of Example A has a MgCl2 to EADC to Ti molar ratio of 40 / 12 / 3 (i.e., MgCl2 / EADC / Ti).

[0106] Comparative Examples 1-3: Batch copolymerization in the presence of a catalyst system without metal-ligand complexes as donor compounds.

[0107] For Comparative Examples 1, 2, and 3 (CE1, CE2, CE3), the pre-catalyst composition of Example A, which does not have a metal-ligand complex as a donor compound, was used as a comparative pre-catalyst for batch reactor copolymerization of ethylene monomer and 1-octene comonomer in a stirred one-gallon reactor. 250 g of 1-octene (C8) and 1330 g of ISOPAR were charged into the reactor. TM E isoparaffin solvent (total 1580 g, including 1-octene comonomer and solvent). The reactor was heated to 190 °C and then saturated with ethylene in the presence of 40 mmol of hydrogen.

[0108] For CE1, donor compounds containing metal-ligand complexes are not used. A certain amount of the pre-formed catalyst composition prepared in Example A and a co-catalyst solution including triethylaluminum (TEA) are mixed in a top-mounted injection vessel for approximately 2 minutes before being injected into the reactor. For CE1, a certain amount of the pre-formed catalyst composition from Example A is added such that the reaction mixture comprises a titanium loading of 1.5 micromoles (μmol) of titanium, and a certain amount of TEA is added such that the molar ratio of TEA to Ti in the reaction mixture is 10 mol / mol.

[0109] For CE2 and CE3, a certain amount of the pre-formed catalyst composition of Example A is added, such that the reaction mixture includes a titanium loading of 4.0 μmol of titanium, and a certain amount of TEA is added, such that the molar ratio of TEA to Ti in the reaction mixture is 15 mol / mol.

[0110] The reactor pressure was maintained at 450 psi (3102.6 kPa, where 1 psi = 6.895 kPa) using an ethylene flow rate to compensate for ethylene consumption during polymerization. After a 10-minute reaction time, the bottom valve of the reactor was opened, and the reactor contents were transferred to a glass vessel. The mixture was then poured onto a Mylar-lined tray, cooled, and allowed to stand overnight in a fume hood to remove most of the solvent via evaporation. The ethylene-based polymers from Comparative Examples 1–3 were then dried in a vacuum oven.

[0111] The catalyst efficiency (Cat.Eff.), weight-average molecular weight (Mw) of the ethylene-based polymer produced, and weight percentage (C8 wt%) of the comonomers produced in the comparative catalyst systems CE1-CE3 were evaluated according to the test methods described herein, and the results are reported in Tables 1, 2, and 3 below, respectively.

[0112] Examples 1-3: Batch copolymerization in the presence of a heterogeneous pre-catalyst including titanium tetraisopropoxide as a metal-ligand complex donor compound.

[0113] For Examples 1-3 (E1, E2, and E3), the catalyst from Example A was used by reacting it with titanium tetraisopropoxide (Ti(O)) before preforming. i A heterogeneous precatalyst prepared by contacting a metal-ligand complex donor compound with Pr4) was used for batch reactor copolymerization of ethylene monomer and 1-octene comonomer in a stirred one-gallon reactor. Initially, 250 g of 1-octene and 1330 g of ISOPAR were charged into the reactor. TM E isoparaffin solvent (total 1580 g, including 1-octene comonomer and solvent). The reactor was heated to 190 °C and then saturated with ethylene in the presence of 40 mmol hydrogen.

[0114] The heterogeneous precatalyst was then prepared by contacting the pre-formed catalyst composition from Example A with a metal-ligand complex. For Examples 1-3, Ti(O) was used. i Pr)4 was used as a metal-ligand complex donor compound. Ti(O) i Pr)4 in ISOPAR TM A solution in an isoalkane solvent (E) was added to a certain amount of the pre-formed catalyst composition of Example A. For each of Examples 1-3, Ti(O) in the pre-formed catalyst was provided in the donor / Ti molar ratio as shown in Table 1. i The amount of Pr)4 relative to the amount in titanium.

[0115] For examples 1 and 2, Ti(O) iPr)4 solution was added to the pre-formed catalyst composition of Example A and mixed for about 2 minutes to prepare the heterogeneous pre-catalyst. Then, a TEA co-catalyst solution was added to the heterogeneous pre-catalyst, and the contents were mixed for about 2 minutes. The catalyst system containing the mixture of the heterogeneous pre-catalyst and TEA was then injected into the reactor. For Example 3, Ti(O)4 solution was added to the pre-formed catalyst composition of Example A. i The Pr)4 donor compound was added to the pre-formed catalyst composition of Example A, and the mixture was aged for 24 hours to produce a heterogeneous pre-catalyst. For each of Examples 1-3, the Ti loading, TEA to Ti molar ratio, and donor compound to Ti molar ratio in the pre-formed catalyst of Example A in the catalyst system are provided in Table 1. As used throughout the examples, Ti loading refers to the amount of Ti from the titanium material in the pre-formed catalyst composition and excludes any Ti added as a metal-ligand complex electron donor compound. Additionally, the TEA to Ti molar ratio refers to the ratio of TEA to Ti from the titanium material in the pre-formed heterogeneous pre-catalyst excluding Ti added as a metal-ligand complex electron donor compound.

[0116] The reactor pressure was maintained at 450 psi (3102.6 kPa) using ethylene flow to compensate for ethylene consumption during copolymerization. After a 10-minute reaction time, the bottom valve of the reactor was opened, and the reactor contents were transferred to a glass vessel. The mixture was then poured onto a Mylar-lined tray, cooled, and allowed to stand overnight in a fume hood to remove most of the solvent via evaporation. The ethylene-based polymer was then dried in a vacuum furnace.

[0117] The catalyst efficiency (Cat.Eff.), weight-average molecular weight (Mw; by GPC) of the ethylene-based polymers produced, and the weight percentage of comonomers (C8 wt%; by GPC) of the ethylene-based polymers produced were evaluated according to the test methods described herein, and the results are reported in Table 1 below. Δ(Mw) and Δ(C8 wt%) in Table 1 represent the changes in Mw and C8 wt% for each of E1-E3 relative to Comparative Example CE1, respectively.

[0118] Table 1

[0119]

[0120] As shown in Table 1, compared with Mw of CE1, the metal-ligand complex Ti(O) i Introducing Ti(O)₄ as an electron donor into the polymerization reaction significantly increases the Mw of ethylene-based polymers in the E1-E3 stages by at least 19%. Compared to CE1 polymers, the addition of Ti(O)₄ significantly increases the Mw. iThe introduction of Pr)4 as an electron donor also caused a significant reduction in the content of comonomers in ethylene-based polymers of E1-E3 by at least 18% or more.

[0121] The results in Table 1 also show that, compared to E1, increasing the donor amount in E2 increases Mw, and compared to the ethylene-based polymer of E1, decreasing the comonomer content of the ethylene-based polymer of E2. Additionally, metal-ligand complexes (e.g., Ti(O)2) can be added in various ways. i Pr)4) is introduced into polymerization reactions. For example, E3 indicates metal-ligand complexes (e.g., Ti(O) i Pr)4) can be incorporated into the heterogeneous pre-catalyst and aged for a period of time, then combined with the co-catalyst just before the polymerization reaction. Compared with polymers produced using the comparative catalyst of CE1 and polymers produced using E1 in which the donor compound is contacted with the pre-catalyst for about 2 minutes, the ethylene-based polymers of E3 exhibit higher Mw and lower comonomer content.

[0122] Example 4-8: Batch copolymerization in the presence of a heterogeneous pre-catalyst including vanadium isopropoxide as a metal-ligand complex donor compound.

[0123] For Examples 4-8 (E4, E5, E6, E7, and E8), vanadium isopropoxide (VO(O)) was used. i Pr)3) is used as a metal-ligand complex donor compound in a heterogeneous pre-catalyst. The copolymerization reactions of Examples 4-8 were carried out according to the methods previously described with respect to Examples 1-3, but with VO(O) i Pr)3 replaces Ti(O) i Pr)4 is a metal-ligand complex.

[0124] In Example 4-8, VO(O) i Pr)3 in ISOPAR TM A solution in an isoparaffin solvent was added to the pre-formed catalyst composition of Example A to produce a heterogeneous pre-catalyst. For each of the heterogeneous pre-catalysts in Examples 4-8, VO(O) in the pre-formed catalyst composition of Example A was provided in the donor / Ti molar ratio as shown in Table 2. i The amount of Pr)3 relative to the amount of titanium.

[0125] For Examples 4-8, VO(O) was added immediately before the TEA co-catalyst was added and the catalyst system was injected into the reactor. i Pr)3 solution was added to the pre-formed catalyst composition of Example A and mixed for about 2 minutes to produce a heterogeneous pre-catalyst.

[0126] The catalyst efficiency (Cat.Eff.), the Mw of the ethylene-based polymer produced, and the C8 wt% of the ethylene-based polymer produced for the catalyst systems of Examples 4-8 were evaluated according to the test methods described herein. The results for Examples 4-8 and CE2 are reported in Table 2 below. The C8 wt% of Example 4 was not determined. Δ(Mw) and Δ(C8 wt%) in Table 2 were calculated as a comparison between each of Examples 4-8 and CE2.

[0127] Table 2

[0128]

[0129] As shown in Table 2, VO(O i Pr)3 can also be used as an electron donor compound in the catalyst system to increase Mw and reduce the comonomer content of the ethylene-based polymer produced by the catalyst system. As shown in Table 2, the Mw of the ethylene-based polymers produced by the catalyst systems of E4-E8 is at least 5% greater than the Mw of the ethylene-based polymer produced by CE2. With VO(O) i The E5-E8 catalyst system with Pr)3 donor compounds also caused a reduction in C8 wt%. The ethylene-based polymers produced by the E5-E8 catalyst system exhibited a comonomer weight percentage that was at least 17% lower than that of the ethylene-based polymers produced by CE2.

[0130] VO(O i Pr)3 donor compounds can also increase catalyst efficiency at low donor / Ti ratios. For example, in E4-E6, VO(O) at donor / Ti ratios of 2.0 or lower... i The catalyst efficiency of Pr)3 is at least 0.50 × 10⁻⁶. 6 This is higher than the efficiency of CE2 catalyst systems that do not include donor compounds. The catalyst efficiency of E4-E6 catalyst systems with a donor / Ti ratio of 2.0 or lower is also substantially higher than that of systems with the same donor / Ti ratio but utilizing Ti(O) i Efficiency of E1-E3 catalyst systems with Pr)4 as the donor compound (Table 1).

[0131] Examples 9-12: Batch copolymerization in the presence of a heterogeneous pre-catalyst including vanadium propanol oxide as a metal-ligand complex donor compound.

[0132] For Examples 9-12 (E9, E10, E11, and E12), vanadium propanol oxide (VO(O)) was used. nPr)3) is used as a metal-ligand complex donor compound in a heterogeneous pre-catalyst. The copolymerization of E9-E12 is carried out according to the previous method relative to E4-E8, but with VO(O) n Pr)3 replaces VO(O) i Pr)3 is used as a metal-ligand complex. In E9-E12, VO(O) n Pr)3 in ISOPAR TM A solution in an isoalkane solvent (E) is added to the pre-formed catalyst composition of Example A to produce a heterogeneous pre-catalyst. For each of E9-E12, VO(O) in the heterogeneous pre-catalyst is provided in the donor / Ti molar ratio as shown in Table 3. n The amount of Pr)3 relative to the amount of titanium.

[0133] For E9-E12, VO(O) should be added immediately before adding the TEA co-catalyst and injecting the catalyst system into the reactor. n Pr)3 solution was added to the pre-formed catalyst composition of Example A and mixed for approximately 2 minutes to prepare a heterogeneous pre-catalyst. The catalyst efficiency (Cat.Eff.), the Mw of the produced ethylene-based polymer, and the C8 wt% of the produced ethylene-based polymer for the E9-E12 catalyst systems were evaluated according to the test methods described herein. The results for E9-E12 and CE3 are reported in Table 3 below. Δ(Mw) and Δ(C8 wt%) in Table 3 are calculated as a comparison of each of E9-E12 with CE3.

[0134] Table 3

[0135]

[0136] VO(O n Pr)3 can be compared to VO(O) i Pr)3 is a more efficient electron donor compound, such as that derived from VO(O) i Compared to ethylene-based polymers containing heterogeneous pre-catalysts produced with Pr)3 at the same donor / Ti ratio (E4-E8 in Table 2), VO(O) n The larger increase in Mw and the larger decrease in C8 wt% are shown in the ethylene-based polymers (E9-E12 in Table 3) produced by Pr)3 containing heterogeneous pre-catalysts. VO(O n Pr)3 donor compounds can also increase catalyst efficiency at low donor / Ti ratios. For example, at a donor / Ti ratio of 1.0, VO(O) n The catalyst efficiency of the E9 catalyst system of Pr)3 is 0.60 × 10⁻⁶. 6This is significantly greater than the catalyst efficiency of the CE3 catalyst system.

[0137] Comparative Example 4: Continuous copolymerization in the absence of a catalyst system with a metal-ligand complex donor compound.

[0138] In Comparative Example 4 (CE4), continuous copolymerization of ethylene-based polymers was carried out in a continuous solution polymerization process using a comparative catalyst system that does not include metal-ligand complex donor compounds. The continuous solution polymerization process included a liquid-insulated and continuous stirred tank reactor (CSTR). Each reactor included independently controlled feeds of all solvent, monomer, comonomer, hydrogen, and catalyst system components. The temperature of the total feed stream (including solvent, monomer, comonomer, and hydrogen) to the reactor was controlled by passing the total feed stream through a heat exchanger before it was introduced into the reactor. The total feed stream to the reactor was injected into the reactor at one location. The catalyst system components were injected into the reactor separately from the other feeds. Agitators in the reactor were used for continuous mixing of the reactants. An oil bath provided additional fine-tuning of the reactor temperature control.

[0139] Ethylene monomer, 1-octene comonomer, and process solvent (Shell Chemicals SBP 100 / 140) were purified with molecular sieves before being introduced into the reactor. Hydrogen was dried with molecular sieves. The feed streams of monomer, solvent, and comonomer were pressurized to a pressure greater than the reaction pressure via a mechanical compressor. The monomer, comonomer, solvent, and hydrogen streams were then combined and introduced into the reactor. The individual components of the catalyst system were manually diluted in batches with purified solvent / diluent and pressurized to a pressure greater than the reaction pressure. For CE4, the comparative catalyst systems included the pre-formed catalyst composition of Example A and TEA as a co-catalyst. For CE4, no metal-ligand complex donor compound was added to the pre-formed catalyst composition of Example A. All reaction feed flow rates were measured using mass flow meters and independently controlled by metering pumps. The reactor conditions for CE4 are provided in Table 4 below.

[0140] The final reactor effluent is passed into a region where water is added and reacts with it to deactivate the catalyst system. After catalyst deactivation, the reactor effluent is passed into a volatilization system to remove ethylene-based polymers from non-polymer streams (e.g., excess monomers or comonomers, solvents, catalysts, etc.). The non-polymer streams are removed from the system, and the isolated polymer melt is granulated and collected. The catalyst efficiency (Cat.Eff.) of the comparative catalyst system for CE4 is evaluated according to the test methods described herein, and the density, melt index (I2), Mw, and C8wt% of the ethylene-based polymer produced in CE4 are evaluated. The results for CE4 are provided in Table 4 below.

[0141] Examples 13 and 14: Continuous copolymerization in the presence of a heterogeneous pre-catalyst including a metal-ligand complex donor compound.

[0142] For Examples 13 and 14 (E13 and E14), according to embodiments of this disclosure, copolymerization of ethylene-based polymers was carried out in a continuous solution polymerization process using a heterogeneous pre-catalyst comprising a metal-ligand complex donor compound. The ethylene-based polymers of E13 and E14 were manufactured according to a solution polymerization process previously described in CE4. For E13 and E14, the metal-ligand complex and pre-catalyst composition of Example A were fed into a static mixer and mixed for approximately 2 minutes to prepare the heterogeneous pre-catalyst.

[0143] For E13, the metal-ligand complex is vanadium propoxide (VO(O)). n Pr)3), the donor / Ti ratio is 2.32, and the TEA / Ti ratio is 8.00. For E14, the metal-ligand complex used is titanium isopropoxide (Ti(O)3). i Pr)4), the donor / Ti ratio (i.e., the ratio of donor to Ti in the preformed catalyst composition from Example A) was 1.70, and the TEA / Ti ratio (i.e., the ratio of TEA to Ti in the preformed catalyst composition from Example A) was 7.82. Process conditions for E13 and E14 are provided in Table 4 below. The catalyst efficiency (Cat.Eff.) of the catalyst systems for E13 and E14 was evaluated according to the methods disclosed herein, and the density, melt index (I2), Mw, and C8 wt% of the ethylene-based polymers produced in E13 and E14 were evaluated. Results are provided in Table 4 below. Δ(Mw) and Δ(C8 wt%) in Table 4 were calculated as a comparison of E13 and E14 with CE4.

[0144] Table 4

[0145]

[0146] As shown in Table 4, in continuous solution polymerization reactions under similar reaction conditions, ethylene-based polymers produced by including metal-ligand complexes in the heterogeneous pre-catalyst have a larger Mw and a smaller C8 wt% compared to those produced using the comparative catalyst system of CE4, such as in E13 and E14.

[0147] Example B: Preparation of preformed heterogeneous precatalysts including heat-treated MgCl2 components from Examples 15-17 and Comparative Example 5.

[0148] In Example B, a pre-formed heterogeneous pre-catalyst incorporating a heat-treated MgCl2 component was synthesized for incorporation into the catalyst systems of Examples 15-18. The MgCl2 component was prepared via ISOPAR... TM The MgCl2 slurry was first synthesized by reacting butyl ethyl magnesium in an E-isoparaffin solution with hydrochloric acid gas to produce 0.20 M MgCl2 slurry. The MgCl2 slurry was stored and handled in a nitrogen-purged glove box to avoid contamination by moisture and oxygen. The MgCl2 slurry was heat-treated using a 5.9 L (L) Parr reactor. 2 L of MgCl2 slurry was loaded into the reactor via an airtight transfer container, ensuring the MgCl2 was not exposed to air or moisture. N2 atmosphere was used for reactor line purging and isolation. The reactor was then heated to 190 °C for 1 hour using a heating mantle. Heating of the reactor was controlled by a stepper controller, with a heating time of approximately one hour (from room temperature to 190 °C). After the specified heating time, the reactor was allowed to cool to room temperature over approximately 3 hours. During the heating process, the contents of the reactor were agitated at 100 rpm. Temperature variations were controlled within ±2 °C. After the reactor is cooled to room temperature, the slurry containing the heat-treated MgCl2 is transferred back to the glove box using an airtight transfer container to prevent exposure to air and / or moisture.

[0149] The slurry containing heat-treated MgCl2 was then used to produce the pre-formed heterogeneous pre-catalyst for Example B. In a N2-purged glove box, ethylaluminum dichloride (EADC, Aldrich, in hexane 1.0 M) (chlorinating agent) and titanium tetraisopropoxide (Ti(O)) were reacted according to the following method. i Pr)4, Aldridge, in ISOPAR TM To produce the pre-formed heterogeneous pre-catalyst of Example B, 0.125 M (titanium) in an isoparaffin solvent was sequentially added to a slurry containing heat-treated MgCl2. For the pre-formed heterogeneous pre-catalyst of Example B, 10 mL of heat-treated MgCl2 slurry was maintained in a capped glass vial with constant stirring. On the first day, 0.301 mL of 1.0 M EADC solution was added to the heat-treated MgCl2 slurry, and the resulting slurry, including the heat-treated MgCl2 component and EADC, was stirred overnight. On the second day, 0.603 mL of 0.125 M Ti(O) was added. i The Pr)4 solution was prepared and the resulting slurry was stirred overnight. The pre-formed heterogeneous pre-catalyst of Example B was prepared for use on the third day. The pre-formed heterogeneous pre-catalyst of Example B comprised a 6:40 molar ratio of EADC to MgCl2 (i.e., 6 moles of EADC for every 40 moles of MgCl2) and a 1.5:40 molar ratio of Ti to MgCl2 (i.e., 1.5 moles of Ti(O) for every 40 moles of MgCl2).i Pr)4).

[0150] Example C: Comparative examples 5-9 show the preparation of pre-formed catalysts using untreated MgCl2.

[0151] The comparative pre-formed catalyst of Example C was produced without heat treatment of MgCl2. The comparative pre-formed catalyst of Example C was produced via ISOPAR... TM The MgCl2 slurry was first synthesized by reacting butyl ethyl magnesium in solution E with hydrochloric acid gas to produce 0.20 M MgCl2 slurry. The MgCl2 slurry was stored in a nitrogen-purged glove box and treated to avoid contamination by moisture and oxygen. Untreated MgCl2 slurry.

[0152] In a glove box purged with N2, ethylaluminum dichloride (EADC, Aldrich, in hexane 1.0M) (chlorinating agent) and titanium tetraisopropoxide (Ti(O)) are reacted according to the following method. i Pr)4, Aldridge, in ISOPAR TM To produce the comparative pre-formed catalyst of Example C, 0.125 M (titanium material) in an isoparaffin solvent was sequentially added to a MgCl2 slurry. For the comparative pre-formed catalyst of Example C, 10 mL of MgCl2 slurry (untreated) was maintained in a capped glass vial under constant stirring.

[0153] On the first day, 0.600 mL of 1.0 M EADC solution was added to the MgCl2 slurry, and the resulting slurry, including the MgCl2 component and EADC, was stirred overnight. On the second day, 1.199 mL of 0.125 M Ti(O) solution was added. i The Pr)4 solution was prepared and the resulting slurry was stirred overnight. The comparative pre-formed catalyst of Example C was prepared for use on the third day. The comparative pre-formed catalyst of Example C consisted of a 12:40 molar ratio of EADC to MgCl2 (i.e., 12 moles of EADC for every 40 moles of MgCl2) and a 3.0:40 molar ratio of Ti to MgCl2 (i.e., 3 moles of Ti(O) for every 40 moles of MgCl2). i Pr)4).

[0154] Examples 15-18: Batch copolymerization in the presence of a heterogeneous pre-catalyst produced from the pre-shaped heterogeneous pre-catalyst of Example B.

[0155] For Examples 15-17 (E15, E16, and E17), batch copolymerization of ethylene and 1-octene was carried out in the presence of a heterogeneous pre-catalyst, comprising heat-treated MgCl2 and a metal ligand complex donor compound, as described in Example B. The batch copolymerization was conducted in a 2L Parr batch reactor. The reactor was heated by an electrically heated mantle and cooled by internally meandering cooling coils using water. A tipple valve was fitted at the bottom of the reactor for draining the reactor contents into a pre-filled catalyst inactivation solution (e.g., from BASF). Organic phosphite processing stabilizers, from BASF A 5 mL mixture of antioxidant and toluene is placed in a stainless steel decanter. Under continuous N2 purging, the decanter is drained into a discharge tank. All solvent used for copolymerization or catalyst replenishment is passed through a purification column to remove impurities. The solvent is passed through two columns: the first containing A2 alumina, and the second containing reduced copper on alumina (Q5 reactant). Ethylene is passed through two columns: the first containing A2O4 alumina and... Molecular sieve, the second one contains reactant Q5. N2 passes through alumina containing A2O4, A single column of molecular sieves and Q5 reactants. The reactor was initially filled with 664g of ISOPAR from a separate tank. TM E solvent and 134±2 g of 1-octene were loaded and filled to the load set point on the Ashcroft differential pressure sensor. Then, after adding the solvent, 14.8±0.3 mmol of hydrogen was added, and the reactor was heated to 190 °C. Then, when the reaction pressure (i.e., 475 psi) was reached at the reaction temperature, 56±1 g of ethylene was added to the reactor. The additional ethylene addition during the polymerization reaction was monitored by a micro-flowmeter.

[0156] The pre-formed heterogeneous pre-catalyst of Example B and a solution of the metal-ligand complex in a hydrocarbon diluent were transferred to a 5 mL glass vial to produce heterogeneous pre-catalysts for E15–E17. For E15, the heterogeneous pre-catalyst comprised 1 molar equivalent of vanadium propoxide (VO₂O₃). n Pr)3) as a metal-ligand complex. For E16, the heterogeneous pre-catalyst comprises 2 molar equivalents of (VO(O) n Pr)3) as a metal-ligand complex. For E17, the heterogeneous pre-catalyst comprises 3 molar equivalents of titanium tetraisopropoxide (Ti(O)). i Pr)4) is a metal-ligand complex.

[0157] For each of E15-E17, the heterogeneous pre-catalyst is then placed into a 20 mL syringe with an 18-gauge needle. The vial is rinsed with solvent, and the rinse solution is also placed into the syringe. The syringe is capped with a vial sealed with a double-ended septum for delivery to the batch reactor outside the glove box.

[0158] The co-catalyst solution of TEA in solvent was placed into a separate syringe. The catalyst system solution (heterogeneous pre-catalyst and TEA) was in a separate syringe and injected within minutes after preparation. The heterogeneous pre-catalyst was prepared next, but injected first, and the TEA solution was rinsed three times (2.5, 2.5, 5 mL).

[0159] Under a flow of N2, the catalyst system components were injected into a spray tank attached to the reactor. The mixture of the two solutions was maintained in the spray tank for 5 minutes, and then introduced into the reactor at a pressure differential of 150 psi after reaching the reactor set point. The amounts of the metal-ligand complex donor compound and the TEA cocatalyst were set based on the amount of Ti present in the pre-formed heterogeneous pre-catalyst of Example B (i.e., 1.4 μmol), and are provided in Table 5 below.

[0160] After the catalyst system is injected, the reaction is initiated to produce an ethylene-based polymer. The reaction mixture is collected for analysis in a stainless steel pan to remove the solvent. The reactor is then subjected to 850 g of ISOPAR at a temperature between 140°C and 160°C. TM E solvent was washed twice. The first wash was collected and combined with the reaction mixture. Ethylene-based polymer samples from each instance were air-dried overnight to remove most of the solvent and then placed in a vacuum furnace under N2 to further remove any entrapped solvent. The vacuum furnace was designed to perform the following operation: three cycles between a nitrogen flow of 5 minutes and a vacuum to 40 Torr, increasing the temperature to 80 °C at 1 °C / min and holding under vacuum for three hours, then increasing to 140 °C and holding for 4 hours. The Mw, melt index I2, high density fraction (HDF wt%), and C8 wt% of the cooled ethylene-based polymers from E15–E17 were then analyzed according to the test methods described herein. The results are presented in Table 5 below.

[0161] Comparative Examples 5 and 6: Batch copolymerization in the presence of a catalyst before the preformed heterogeneous phase of Examples C and B.

[0162] For Comparative Examples 5 and 6 (CE5 and CE6), batch copolymerization of ethylene and 1-octene was carried out using a pre-forming catalyst without metal ligand complexes. For CE5, copolymerization was carried out using a pre-forming heterogeneous pre-forming catalyst of heat-treated MgCl2 from Example B. For CE6, copolymerization was carried out using a comparative pre-forming catalyst of Example C including untreated MgCl2. Batch copolymerization of CE5 and CE6 was carried out according to the methods described previously in E15-E17. In CE5 and CE6, no metal-ligand complexes were added to the pre-forming catalyst. For each of CE5 and CE6, the pre-forming catalyst was injected into a spray tank without the addition of a metal-ligand complex as a donor compound. Ethylene-based polymers of CE5 and CE6 were collected according to the test methods described herein, and their Mw, melt index I2, HDF, and C8 wt% were evaluated. The results are presented in Table 5.

[0163] Comparison of Examples 15-17 (E15-E17) with Comparative Examples 5 and 6 (CE5 and CE6).

[0164] Table 5 below provides the compositional parameters of the catalyst systems E15-17, CE5, and CE6, as well as the Mw, I2, HDF, and C8 wt% of the ethylene-based polymers produced in E15-17, CE5, and CE6. Δ(Mw), Δ(HDF), and Δ(C8 wt%) in Table 5 are calculated as a comparison of each of E15-E17 and CE5 with CE6. In Table 5, the Ti loading in the reactor refers to the amount of Ti associated with the pre-formed catalyst and excludes any amount of Ti contributed by electron-donating compounds.

[0165] Table 5: Comparison of ethylene-based polymers of E15-E17 with ethylene-based polymers of CE5 and CE6

[0166] Sample ID E15 E16 E17 CE5 CE6 Preformed heterogeneous pre-catalyst Example B Example B Example B Example B Example C Metal-ligand complex donors <![CDATA[VO(O n Pr)3]]> <![CDATA[VO(O n Pr)3]]> <![CDATA[Ti(O i Pr)4]]> -- -- Ti loading (μmol) 1.40 1.40 1.40 1.40 1.40 Donor / Ti (mol / mol) 1 2 3 -- -- TEA / Ti(mol / mol 15 15 15 8 8 Mw (Dalton) 132370 142570 138325 125672 100301 Δ(Mw)(%) 32 42 38 25 -- <![CDATA[Melt Index I2]]> 0.64 0.52 0.57 1.02 1.80 HDF (wt%) 43.91 47.75 47.22 36.44 13.98 Δ(HDF)(%) 214 242 238 161 -- C8 wt% 5.08 4.38 4.77 6.51 9.10 Δ(C8 wt%) -44 -52 -48 -28 --

[0167] A comparison between CE5 and CE6 shows that, in the presence of a pre-forming catalyst including heat-treated MgCl2 (e.g., the pre-forming heterogeneous pre-catalyst of Example B used in CE5), the ethylene-based polymers produced exhibit larger Mw, larger HDF, reduced melt index (I2), and reduced comonomer content (C8 wt%) compared to those produced in the presence of a comparative pre-forming catalyst with untreated MgCl2 (e.g., the comparative pre-forming catalyst of Example C used in CE6). For example, even though catalyst system CE5 has a lower Ti / Mg molar ratio than catalyst system CE6 (0.0375 vs. 0.075), the ethylene-based polymers produced in CE5 exhibit a 25% increase in Mw, a 161% increase in HDF, a 43% decrease in I2, and a 28% decrease in C8 wt% compared to the ethylene-based polymers produced in CE6. For Ziegler-Natta catalysts, it is generally desirable to produce (co)polymers with lower Mw, lower HDF, higher I2 and higher C8 wt% by containing lower Ti.

[0168] A comparison of E15 and E16 with CE5 shows that, compared to ethylene-based polymers produced using the pre-formed heterogeneous pre-catalyst of Example B, which lacks a metal-ligand complex donor compound, the inclusion of VO(O) in the heterogeneous pre-catalyst results in significantly higher yields. n Pr)3 metal-ligand complexes, as donor compounds, can further increase the Mw and HDF of ethylene-based polymers and reduce I2 and C8wt%. A comparison of E15 and E16 shows that VO(O) in the heterogeneous pre-catalyst... n A higher molar ratio of Pr)3 metal-ligand complex to titanium (i.e., donor / Ti molar ratio) can further increase the Mw and HDF of the resulting ethylene-based polymer and decrease I2 and C8 wt%. A comparison of E17 with CE5 shows that, compared to the catalyst without Ti(O) in the pre-formed heterogeneous catalyst (CE5),... i Compared to the production of ethylene-based polymers using Pr)4 metal-ligand complexes as donor compounds, the use of Ti(O)4 in heterogeneous pre-catalysts... i Pr)4 metal-ligand complexes, as donor compounds, and heat-treated MgCl2 can also increase the Mw and HDF of ethylene-based polymers (E17) and decrease I2 and C8 wt%.

[0169] Example D: Preparation of preformed heterogeneous precatalysts including heat-treated MgCl2 components from Examples 18 and 19.

[0170] In Example D, a pre-formed heterogeneous pre-catalyst incorporating a heat-treated MgCl2 component was synthesized for incorporation into the catalyst systems of Examples 18 and 19. The pre-formed heterogeneous pre-catalyst of Example D was produced according to the method described previously in Example B. Heat-treated MgCl2 slurry, EADC, and Ti(O) were used. i The relative amounts of Pr)4 were modified so that the heterogeneous pre-catalyst of Example D had a thermally treated MgCl2 and EADC and Ti(O)4 ratio of 40:12:3. i The molar ratio of Pr)4 is (i.e., 12 moles of EADC per 40 moles of MgCl2 and 3.0 moles of Ti(O) per 40 moles of MgCl2). i Pr)4).

[0171] Example E: Preparation of preformed heterogeneous precatalysts including heat-treated MgCl2 components from Examples 20 and 21.

[0172] In Example E, a pre-formed heterogeneous pre-catalyst incorporating a heat-treated MgCl2 component was synthesized for incorporation into the catalyst systems of Examples 20 and 21. The pre-formed heterogeneous pre-catalyst of Example E was produced according to the method previously described in Example B. Heat-treated MgCl2 slurry, EADC, and Ti(O) were used. i The relative amount of Pr)4 was modified so that the pre-formed heterogeneous pre-catalyst of Example E had a thermally treated MgCl2 and EADC and Ti(O)4 ratio of 40:6.8:1.7. i The molar ratio of Pr)4 is (i.e., 6.8 moles of EADC per 40 moles of MgCl2 and 1.7 moles of Ti(O) per 40 moles of MgCl2). i Pr)4).

[0173] Examples 18-21: Batch copolymerization in the presence of a heterogeneous pre-catalyst including metal-ligand complex donor compounds.

[0174] For Examples 18-21 (E18, E19, E20, and E21), the batch copolymerization of ethylene and 1-octene is carried out in the presence of a catalyst system comprising one of the pre-formed heterogeneous pre-catalysts of Examples D or E, wherein a metal-ligand complex is added as a donor compound. For each of E18, E19, E20, and E21, the metal-ligand complex donor compound and the initial pre-formed heterogeneous pre-catalyst are provided in Table 6 below. Table 6 also provides the molar ratio of the metal-ligand complex to Ti in the pre-formed heterogeneous pre-catalyst in the catalyst systems of E18-E21. For E18-E21, the molar ratio of TEA to Ti in the pre-formed pre-catalyst is 15:1.

[0175] For E18-E21, the batch copolymerization of ethylene and 1-octene is carried out in a one-gallon stirred reactor, wherein the reactor is charged with 250 g of 1-octene and 1330 g of ISPOAR. TM E isoparaffin solvent, totaling 1580 g. The reactor was heated to 190 °C and then saturated with ethylene in the presence of 40 mmol hydrogen. The heterogeneous precatalyst was prepared by adding a metal-ligand complex to the pre-formed heterogeneous precatalyst of Example D or Example E and mixing for 2 minutes.

[0176] For E18 and E20, use titanium tetraisopropoxide (Ti(O)) i Pr)4) is used as a metal-ligand complex. For E19 and E21, vanadium butanol oxide (VO(O)) is used. n Bu)3) as a metal-ligand complex. Table 6 below provides the molar ratio of the metal-ligand complex to Ti from the pre-formed heterogeneous catalyst in each of the catalyst systems in E18-E21.

[0177] As previously described in E15-E17, the heterogeneous pre-catalyst (including metal-ligand complexes) and TEA co-catalyst solution were separately placed in syringes and injected into a top-mounted injection tank. For each example, the catalyst system, including the heterogeneous pre-catalyst and TEA co-catalyst, was mixed in the injection tank for approximately 2 minutes before injection into the reactor. The reactor pressure was maintained at 450 psi (3102 kPa) with an ethylene flow rate to compensate for ethylene consumption during polymerization. After a 10-minute reaction time, the bottom valve of the reactor was opened, and the contents were transferred to a glass vessel. The mixture was poured from the glass vessel onto a Mylar-lined tray, cooled, and allowed to stand overnight in a fume hood to remove most of the solvent via evaporation. The resulting ethylene-based polymer was then dried in a vacuum furnace.

[0178] Examples 22-23: Batch copolymerization in the presence of a pre-formed heterogeneous catalyst and a metal-ligand complex donor compound in Example C.

[0179] For Examples 22-23 (E22 and E23), the batch copolymerization of ethylene and 1-octene was carried out in the presence of a heterogeneous pre-catalyst comprising a metal-ligand complex as a donor compound, which was added to the pre-formed heterogeneous pre-catalyst of Example C comprising untreated MgCl2. For E22, tetraisopropoxide titanium (Ti(O)) was added. i Pr)4) as a metal-ligand complex. For E23, vanadium butyrate (VO(O)) was added. nBu)3) as a metal-ligand complex. Table 6 below provides the molar ratios of the metal-ligand complexes to Ti in the catalyst systems of E22 and E23 (from the pre-formed heterogeneous catalyst). The copolymerization of E22 and E23 was carried out according to the methods previously described in E18-E21.

[0180] Comparative Examples 7 and 8: Batch copolymerization of Examples D and E in the presence of a pre-formed heterogeneous catalyst without metal-ligand complex donor compounds.

[0181] For Comparative Examples 7 and 8 (CE7 and CE8), the batch copolymerization of ethylene and 1-octene was carried out in the presence of a catalyst system comprising one of the pre-formed heterogeneous pre-catalysts of Examples D or E having heat-treated MgCl2. The copolymerization of CE7 and CE8 was carried out without the addition of a metal-ligand complex to the catalyst system. The copolymerization of CE7 was carried out using the pre-formed heterogeneous pre-catalyst of Example D, and the copolymerization of CE8 was carried out using the pre-formed heterogeneous pre-catalyst of Example E. The copolymerization of CE7 and CE8 was carried out according to the methods described in E18-E21 above, except that the metal-ligand complex was not included in the heterogeneous pre-catalyst.

[0182] Comparative Example 9: Batch copolymerization in the presence of a catalyst before the preformed heterogeneous phase of Example C.

[0183] For Comparative Example 9 (CE9), the batch copolymerization of ethylene and 1-octene was carried out in the presence of a catalyst system comprising a comparative pre-catalyst containing the pre-catalyst composition of Example C, MgCl2, without heat treatment. The copolymerization of CE9 was carried out without the addition of a metal-ligand complex to the pre-catalyst. The copolymerization of CE9 was carried out according to the methods described in E18-E21 above, except that the metal-ligand complex was not included in the heterogeneous pre-catalyst.

[0184] Evaluation and comparison of ethylene-based polymers in Examples E18-E23 and Comparative Examples CE7-CE9.

[0185] The Mw, C8 wt.%, and HDF of the ethylene-based polymers collected from the copolymers of E18-E23 and CE7-CE9 were evaluated according to the test methods described herein, and the results are presented in Table 6 below. Δ(Mw), Δ(C8 wt.%), and Δ(HDF) of E18, E19, E20, E21, E22, E23, CE7, and CE8 in Table 6 were calculated as changes compared to CE9.

[0186] Table 6

[0187]

[0188] A comparison of ethylene-based polymers CE7, CE8, and CE9 shows that, compared with ethylene-based polymers prepared with a comparative pre-formed heterogeneous pre-catalyst including heat-treated MgCl2 (CE9), the production of ethylene-based polymers (CE7 and CE8) in the presence of a pre-formed heterogeneous pre-catalyst including heat-treated MgCl2 increases the Mw of the ethylene-based polymer, increases HDF, and decreases C8 wt%.

[0189] A comparison of ethylene-based polymers from E22 and E23 with that from CE9 shows that, compared to ethylene-based polymers prepared under the same reactor process conditions using a pre-catalyst that does not include a metal-ligand complex as a donor compound (CE9), including a metal-ligand complex as a donor compound in the heterogeneous pre-catalysts (E22 and E23) increases the Mw of the ethylene-based polymers, increases HDF wt%, and decreases C8 wt%. The increase in Mw and HDF wt% and the decrease in C8 wt% of the ethylene-based polymers can be achieved by including a metal-ligand complex as a donor compound in the heterogeneous pre-catalyst without thermally treating the MgCl2 component.

[0190] A comparison of ethylene-based polymers E18, E22, CE7, and CE9 shows that, compared with ethylene-based polymers of CE9 and E22(Ti(O) i Compared to ethylene-based polymers such as Pr)4 metal-ligand complex (but without heat-treated MgCl2) and CE7 (heat-treated MgCl2 but without metal-ligand complex donor compounds), which have heat-treated MgCl2 and Ti(O) i Pr)4 as a heterogeneous pre-catalyst (E18) as a metal-ligand complex donor compound produces ethylene-based polymers with larger Mw, larger HDF wt%, and reduced C8 wt%. Therefore, including both thermally treated MgCl2 and the metal-ligand complex in the heterogeneous pre-catalyst provides a greater increase in Mw and HDF wt% and a greater decrease in C8 wt% for ethylene-based polymers compared to including either thermally treated MgCl2 or the metal-ligand complex, but not both, in the heterogeneous pre-catalyst. In E20, ethylene-based polymers with lower EADC and Ti contents (MgCl2 / EADC / Ti = 40 / 6.8 / 1.7) are produced in the presence of the pre-catalyst based on Example E, compared to the pre-catalyst of Example D used in E18 (MgCl2 / EADC / Ti = 40 / 6.8 / 1.7). A comparison of ethylene-based polymers E20, E22, CE8, and CE9 shows that increasing the Mw and HDF and decreasing the C8 wt% of ethylene-based polymers can be achieved by including heat-treated MgCl2 and Ti(O)2.i Pr)4 metal-ligand complexes are achieved even when the heterogeneous pre-catalyst is formulated with lower amounts of EADC (chlorinating agent) and Ti (titanium material).

[0191] A comparison of ethylene-based polymers of E19, E23, CE7, and CE9 shows that, compared with ethylene-based polymers of CE9 and E23(VO(O) n Compared to ethylene-based polymers such as Bu(3) metal-ligand complexes but without heat-treated MgCl2 and CE7 (heat-treated MgCl2 but without metal-ligand complex donor compounds), including heat-treated MgCl2 and VO(O) n Bu)3, as a heterogeneous pre-catalyst (E19) for metal-ligand complex donor compounds, produces ethylene-based polymers with larger Mw, larger HDF wt%, and reduced C8 wt%. In E21, compared to the pre-catalyst of Example D used in E19 (MgCl2 / EADC / Ti = 40 / 12 / 3), the presence of a heterogeneous catalyst including the pre-catalyst of Example E produces ethylene-based polymers with a reduced EADC to Ti molar ratio (MgCl2 / EADC / Ti = 40 / 6.8 / 1.7). A comparison of ethylene-based polymers from E21, E23, CE8, and CE9 shows that increasing the Mw and HDF and reducing the C8 wt% of ethylene-based polymers can be achieved by including heat-treated MgCl2 and VO(O) n Bu)3 metal-ligand complexes are achieved, even when the heterogeneous pre-catalyst is formulated with lower amounts of EADC and Ti.

[0192] In a first aspect of this disclosure, the heterogeneous pre-catalyst may comprise titanium material with a specific surface area of ​​at least 100 m². 2 A pre-formed MgCl2 support, chlorinating agent, and metal-ligand complex ( / g). The chlorinating agent may have the structural formula Al(Cl). x (R 1 ) 3-x Or Si(Cl) y (R 1 ) 4-y , where R 1 For (C1-C 30 A hydrocarbon group, where x is 1, 2, or 3, and y is 1, 2, 3, or 4. Metal-ligand complexes may have the structural formula (L). n M(Y) m (XR 2 ) b Where M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR 2It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ( ) Heteroalkyl group; n is 0, 1 or 2; m is 0, 1, 2, 3 or 4; b is 1, 2, 3, 4, 5 or 6; and the metal-ligand complex is generally charge-neutral.

[0193] The second aspect of this disclosure may include a fist-like aspect, wherein the chlorinating agent is selected from ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum dichloride, diisobutylaluminum chloride, and combinations thereof.

[0194] The third aspect of this disclosure may include the first or second aspect, wherein the titanium material is TiCl. 4-c (OR 3 ) c or TiCl 3-d (OR 3 ) d , where R 3 For (C1-C 20 () Hydrocarbon group, c is 0, 1, 2, 3 or 4, and d is 0, 1, 2 or 3.

[0195] The fourth aspect of this disclosure may include the third aspect, wherein the total amount of chlorine in the chlorinating agent is related to the OR in the heterogeneous pre-catalyst. 3 and XR 2 The molar ratio of the total amount is 0.33 to 1.45.

[0196] The fifth aspect of this disclosure may include any one of the first to fourth aspects, wherein the titanium material is selected from TiCl4, TiCl3, TiCl2(OC2H5)2, TiCl2(Oi-C3H7)2, TiCl2(On-C4H9)2, TiCl2(Oi-C4H9)2, TiCl(Oi-C3H7)3, TiCl(On-C4H9)3, TiCl(Oi-C4H9)3, Ti(OC2H5)4, Ti(Oi-C3H7)4, Ti(On-C4H9)4, Ti(Oi-C4H9)4 and Ti(OCH2CH(C2H5)(C4H9))4.

[0197] The sixth aspect of this disclosure may include any one of the first to fifth aspects, wherein the MgCl2 support is the reaction product of an alkyl magnesium compound solution in a hydrocarbon diluent and a chloride source, without the need to separate the hydrocarbon diluent.

[0198] The seventh aspect of this disclosure may include the sixth aspect, wherein the metal-ligand complex is at least partially soluble in the hydrocarbon diluent supported on MgCl2.

[0199] The eighth aspect of this disclosure may include any one of the first to seventh aspects, wherein the molar ratio of the chlorinating agent to MgCl2 in the heterogeneous pre-catalyst is 0.05:1 to 2:1.

[0200] The ninth aspect of this disclosure may include any one of the first to eighth aspects, wherein the molar ratio of titanium material to MgCl2 in the heterogeneous pre-catalyst is from 0.005:1 to 0.25:1.

[0201] In a tenth aspect of this disclosure, the heterogeneous precatalyst may comprise a pre-shaped heterogeneous precatalyst comprising a titanium material and a MgCl2 support. The heterogeneous precatalyst may further comprise components having the structural formula (L). n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ( ) Heteroalkyl group; n is 0, 1 or 2; m is 0, 1, 2, 3 or 4; b is 1, 2, 3, 4, 5 or 6; and the metal-ligand complex is generally charge-neutral.

[0202] The eleventh aspect of this disclosure may include any one of the first to tenth aspects, wherein the metal-ligand complex has the structural formula M(OR) 2 ) e Metal alkoxides, where e is 2, 3, 4, 5 or 6.

[0203] The twelfth aspect of this disclosure may include any one of the first to tenth aspects, wherein the metal-ligand complex has the structural formula M(=O)(OR) 2 ) f Metal oxyalkoxides, wherein f is 1, 2, 3 or 4.

[0204] The thirteenth aspect of this disclosure may include any one of the first to twelfth aspects, wherein M is a transition metal cation.

[0205] The fourteenth aspect of this disclosure may include any one of the first to twelfth aspects, wherein M is a group metal cation.

[0206] The fifteenth aspect of this disclosure may include any one of the first to twelfth aspects, wherein M is vanadium, titanium, scandium, zirconium, niobium, magnesium, or calcium.

[0207] The sixteenth aspect of this disclosure may include any one of the first to thirteenth aspects, wherein the metal-ligand complex comprises at least one of the following: vanadium tripropoxide (V), vanadium tributoxide (V), vanadium triisopropoxide (V), titanium isopropoxide (IV), titanium ethoxide (IV), or a combination thereof.

[0208] The seventeenth aspect of this disclosure may include any one of the first to sixteenth aspects, wherein the pre-catalyst further comprises an additional transition metal compound.

[0209] The eighteenth aspect of this disclosure may include the seventeenth aspect, wherein the additional transition metal compound may be independently selected from zirconium, hafnium, vanadium and chromium.

[0210] The nineteenth aspect of this disclosure may include any one of the first to eighteenth aspects, wherein the heterogeneous pre-catalyst may be prepared by a method comprising: heat-treating magnesium chloride at a temperature above 100°C for at least 30 minutes to form a magnesium chloride component, and then contacting the magnesium chloride component with a titanium material.

[0211] The twentieth aspect of this disclosure may include any one of the first to nineteenth aspects and relates to a catalyst system for olefin polymerization, which may include a heterogeneous precatalyst of any one of the first to nineteenth aspects and a cocatalyst comprising an organoaluminum compound.

[0212] In a twenty-first aspect of this disclosure, a catalyst system for olefin polymerization may include a pre-formed heterogeneous pre-catalyst comprising a titanium material and a MgCl2 support. The catalyst system may further include components having the structural formula (L). n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 The catalyst system may contain a heteroalkyl group; n is 0, 1, or 2; m is 0, 1, 2, 3, or 4; b is 1, 2, 3, 4, 5, or 6; and the metal-ligand complex is generally charge-neutral. The catalyst system may additionally include a cocatalyst comprising an organoaluminum compound.

[0213] The twentieth aspect of this disclosure may include the twentieth aspect, wherein the cocatalyst is selected from alkylaluminum, haloalkylaluminum, haloalkylaluminum, and combinations thereof.

[0214] The twentieth aspect of this disclosure may include any one of aspects twentieth to twentieth to twentieth to twentieth, wherein the polymerization method may include contacting ethylene and optionally one or more α-olefin comonomers with a catalyst system according to any one of aspects twentieth to ...

[0215] The twentieth aspect of this disclosure may include the twentieth aspect, wherein the polymerization method is a solution polymerization method.

[0216] In a twenty-fifth aspect of this disclosure, a method for preparing a heterogeneous pre-catalyst may include contacting a magnesium chloride component with a chlorinating agent, a titanium substance, and a metal-ligand complex. The magnesium chloride component may have a specific surface area of ​​at least 100 m². 2 / g of pre-formed MgCl2 carrier. The chlorinating agent may have the structural formula Al(Cl). x (R 1 ) 3-x Or Si(Cl) y (R 1 ) 4-y , where: R 1 For (C1-C 30 (L) Hydrocarbon group; x is 1, 2, or 3; and y is 1, 2, 3, or 4. Metal-ligand complexes may have the structural formula (L). n M(Y) m (XR 2 ) b Where: M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ( ) Heteroalkyl group; n is 0, 1 or 2; m is 0, 1, 2, 3 or 4; b is 1, 2, 3, 4, 5 or 6; and the metal-ligand complex is generally charge-neutral.

[0217] In a twenty-sixth aspect of this disclosure, a method for preparing a heterogeneous precatalyst may include contacting components (1) and (2) without additional chlorination. Component (1) may be a preformed heterogeneous precatalyst comprising a titanium material and a MgCl2 support. Component (2) may be a material having the structural formula (L). n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein M is a metal cation; each L is a neutral ligand or (=O); each Y is a halide or (Cl-C) 20 )alkyl; each XR 2It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 ( ) Heteroalkyl group; n is 0, 1 or 2; m is 0, 1, 2, 3 or 4; b is 1, 2, 3, 4, 5 or 6; and the metal-ligand complex is generally charge-neutral.

[0218] The twentieth aspect of this disclosure may include the twentieth or twentieth sixteenth aspect, wherein the metal-ligand complex is in a hydrocarbon solution.

[0219] The twentieth aspect of this disclosure may include any one of aspects 25 to 22, which further includes a heat treatment time of at least 30 minutes at a temperature above 100°C.

[0220] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Therefore, this specification is intended to cover modifications and variations of the various embodiments described herein, provided that such modifications and variations fall within the scope of the appended claims and their equivalents.

[0221] In summary, the present invention includes, but is not limited to, the following:

[0222] 1. A heterogeneous pre-catalyst, comprising:

[0223] Titanium materials;

[0224] Specific surface area is at least 100 m² 2 / g of pre-formed MgCl2 carrier;

[0225] It has the structural formula Al(Cl). x (R 1 ) 3-x Or Si(Cl) y (R 1 ) 4-y The chlorinating agent, wherein:

[0226] R 1 For (C1-C 30 hydrocarbon group;

[0227] x is 1, 2, or 3; and

[0228] y is 1, 2, 3 or 4; and

[0229] It has a structural formula (L) n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein:

[0230] M is a metal cation;

[0231] Each L is a neutral ligand or (=O);

[0232] Each Y is a halide or (C1-C) 20 )alkyl;

[0233] Each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 Heterohydrocarbons;

[0234] n is 0, 1, or 2;

[0235] m can be 0, 1, 2, 3, or 4;

[0236] b is 1, 2, 3, 4, 5, or 6; and

[0237] The metal-ligand complex is generally charge-neutral.

[0238] 2. The heterogeneous pre-catalyst according to claim 1, wherein the chlorinating agent is selected from ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum dichloride, diisobutylaluminum chloride, and combinations thereof.

[0239] 3. The heterogeneous pre-catalyst according to item 1 or 2, wherein the titanium material is TiCl 4-c (OR 3 ) c or TiCl 3-d (OR 3 ) d , where R 3 For (C1-C 20 () Hydrocarbon group, c is 0, 1, 2, 3 or 4, and d is 0, 1, 2 or 3.

[0240] 4. The heterogeneous pre-catalyst according to claim 3, wherein the total amount of chlorine in the chlorinating agent is related to the total amount of OR in the heterogeneous pre-catalyst. 3 and XR 2 The molar ratio of the total amount is 0.33 to 1.45.

[0241] 5. The heterogeneous pre-catalyst according to any one of the preceding claims, wherein the titanium material is selected from TiCl4, TiCl3, TiCl2(OC2H5)2, TiCl2(Oi-C3H7)2, TiCl2(On-C4H9)2, TiCl2(Oi-C4H9)2, TiCl(Oi-C3H7)3, TiCl(On-C4H9)3, TiCl(Oi-C4H9)3, Ti(OC2H5)4, Ti(Oi-C3H7)4, Ti(On-C4H9)4, Ti(Oi-C4H9)4 and Ti(OCH2CH(C2H5)(C4H9))4.

[0242] 6. The heterogeneous precatalyst according to any one of the preceding claims, wherein the MgCl2 support is the reaction product of an alkyl magnesium compound solution in a hydrocarbon diluent and a chloride source, without the need to separate the hydrocarbon diluent.

[0243] 7. The heterogeneous pre-catalyst according to any one of the preceding claims, wherein the molar ratio of the chlorinating agent to MgCl2 in the heterogeneous pre-catalyst is 0.05:1 to 2:1.

[0244] 8. The heterogeneous precatalyst according to any one of the preceding claims, wherein the molar ratio of the titanium material to MgCl2 in the heterogeneous precatalyst is from 0.005:1 to 0.25:1.

[0245] 9. A heterogeneous pre-catalyst, comprising:

[0246] Pre-formed heterogeneous pre-catalysts include the following:

[0247] Titanium materials; and

[0248] MgCl2 support; and

[0249] It has a structural formula (L) n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein:

[0250] M is a metal cation;

[0251] Each L is a neutral ligand or (=O);

[0252] Each Y is a halide or (C1-C) 20 )alkyl;

[0253] Each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20) hydrocarbon group or (C1-C 20 Heterohydrocarbons;

[0254] n is 0, 1, or 2;

[0255] m can be 0, 1, 2, 3, or 4;

[0256] b is 1, 2, 3, 4, 5, or 6; and

[0257] The metal-ligand complex is generally charge-neutral.

[0258] 10. The heterogeneous precatalyst according to any one of the preceding claims, wherein the metal-ligand complex has the structural formula M(OR) 2 ) e Metal alkoxides, wherein e is 2, 3, 4, 5, or 6, or having the structural formula M(=O)(OR 2 ) f Metal oxyalkoxides, wherein f is 1, 2, 3 or 4.

[0259] 11. The heterogeneous precatalyst according to any one of the preceding items, wherein M is selected from at least one of the following: vanadium cation, titanium cation, scandium cation, zirconium cation, niobium cation, magnesium cation or calcium cation.

[0260] 12. The heterogeneous precatalyst according to any one of claims 1 to 11, wherein the metal-ligand complex comprises at least one of the following: vanadium tripropanol oxide (V), vanadium tributanol oxide (V), vanadium triisopropanol oxide (V), titanium isopropoxide (IV), titanium ethoxide (IV), or a combination thereof.

[0261] 13. The heterogeneous precatalyst according to any one of the preceding items, which is prepared by a method comprising: heat-treating magnesium chloride at a temperature above 100°C for at least 30 minutes to form the magnesium chloride component, and then contacting the magnesium chloride component with the titanium material.

[0262] 14. A catalyst system for olefin polymerization, the catalyst system comprising:

[0263] The heterogeneous pre-catalyst according to any one of the preceding items; and

[0264] A cocatalyst containing organoaluminum compounds.

[0265] 15. The catalyst system according to claim 14, wherein the co-catalyst is selected from alkylaluminum, haloalkylaluminum, alkylhalide, and combinations thereof.

[0266] 16. A polymerization method comprising contacting ethylene and optionally one or more α-olefin comonomers with a catalyst system according to claim 14 or 15.

[0267] 17. The polymerization method according to item 16, wherein the polymerization method is a solution polymerization method.

[0268] 18. A method for preparing a heterogeneous pre-catalyst, the method comprising contacting a magnesium chloride component with a chlorinating agent, a titanium substance, and a metal-ligand complex, wherein:

[0269] The magnesium chloride component has a specific surface area of ​​at least 100 m². 2 / g of pre-formed MgCl2 carrier;

[0270] The chlorinating agent has the structural formula Al(Cl). x (R 1 ) 3-x Or Si(Cl) y (R 1 ) 4-y ,in:

[0271] R 1 For (C1-C 30 hydrocarbon group;

[0272] x is 1, 2, or 3; and

[0273] y is 1, 2, 3 or 4; and

[0274] The metal-ligand complex has the structural formula (L). n M(Y) m (XR 2 ) b ,in:

[0275] M is a metal cation;

[0276] Each L is a neutral ligand or (=O);

[0277] Each Y is a halide or (C1-C) 20 )alkyl;

[0278] Each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 Heterohydrocarbons;

[0279] n is 0, 1, or 2;

[0280] m can be 0, 1, 2, 3, or 4;

[0281] b is 1, 2, 3, 4, 5, or 6; and

[0282] The metal-ligand complex is generally charge-neutral.

[0283] 19. A method for preparing a heterogeneous pre-catalyst, the method comprising contacting components (1) and (2) without additional chlorination, wherein:

[0284] Component (1) is a pre-formed heterogeneous pre-catalyst comprising the following:

[0285] Titanium materials; and

[0286] MgCl2 support; and

[0287] Component (2) has the structural formula (L). n M(Y) m (XR 2 ) b Metal-ligand complexes, wherein:

[0288] M is a metal cation;

[0289] Each L is a neutral ligand or (=O);

[0290] Each Y is a halide or (C1-C) 20 )alkyl;

[0291] Each XR 2 It is an anionic ligand, where X is a heteroatom or a functional group containing a heteroatom, and R 2 For (C1-C 20 ) hydrocarbon group or (C1-C 20 Heterohydrocarbons;

[0292] n is 0, 1, or 2;

[0293] m can be 0, 1, 2, 3, or 4;

[0294] b is 1, 2, 3, 4, 5, or 6; and

[0295] The metal-ligand complex is generally charge-neutral.

[0296] 20. The method according to any one of items 18 to 19, further comprising a heat treatment time of at least 30 minutes at a temperature above 100°C.

Claims

1. A heterogeneous procatalyst comprising: titanium species; wherein the titanium species is TiCl 4-c (OR 3 ) c or TiCl 3-d (OR 3 ) d wherein R 3 is a (C1-C 20 )hydrocarbyl group, c is 0, 1, 2, 3, or 4, and d is 0, 1, 2, or 3; a specific surface area of at least 100 m 2 / g of pre-formed MgCl2support; chlorinating agent having the structural formula Al(Cl) x (R 1 ) 3-x or Si(Cl) y (R 1 ) 4-y wherein: R 1 is (C1-C 30 )alkyl; x is 1, 2, or 3; and y is 1, 2, 3, or 4; and having the structural formula (L) n M(Y) m (XR 2 ) b metal-ligand complex of the formula: M is a metal cation; each L is a neutral ligand or (=0); each Y is halide or (Ci-C 20 )alkyl; each XR 2 is an anionic ligand, wherein X is a heteroatom or a heteroatom-containing functional group, and R 2 is a (C1-C 20 )hydrocarbyl or (C1-C 20 )heterohydrocarbyl group; n is 0, 1, or 2; m is 0, 1, 2, 3, or 4; b is 1, 2, 3, 4, 5, or 6; and the metal-ligand complex is generally charge neutral; wherein the sum of the total amount of chlorine in the chlorinating agent and the amount of OR 3 and XR 2 is in a molar ratio of 0.33 to 1.

45.

2. The heterogeneous procatalyst of claim 1, wherein the chlorinating agent is selected from the group consisting of ethyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum sesquichloride, isobutyl aluminum dichloride, diisobutyl aluminum chloride, and combinations thereof.

3. The heterogeneous procatalyst of any one of the preceding claims, wherein the titanium species is selected from the group consisting of TiCl4, TiCl3, TiCl2(OC2H5)2, TiCl2(O-i-C3H7)2, TiCl2(O-n-C4H9)2, TiCl2(O-i-C4H9)2, TiCl(O-i-C3H7)3, TiCl(O-n-C4H9)3, TiCl(O-i-C4H9)3, Ti(OC2H5)4, Ti(O-i-C3H7)4, Ti(O-n-C4H9)4, Ti(O-i-C4H9)4, and Ti(OCH2CH(C2H5)(C4H9))4.

4. The heterogeneous procatalyst of any one of the preceding claims, wherein the MgCl2 support is a reaction product of an alkyl magnesium compound solution in a hydrocarbon diluent and a chloride source without isolating the hydrocarbon diluent.

5. The heterogeneous procatalyst of claim 4, wherein the metal-ligand complex is at least partially soluble in the hydrocarbon diluent of the MgCl2 support.

6. The heterogeneous procatalyst of any one of the preceding claims, wherein the molar ratio of the chlorinating agent to MgCl2 in the heterogeneous procatalyst is from 0.05:1 to 2:

1.

7. The heterogeneous procatalyst of any one of the preceding claims, wherein the molar ratio of the titanium species to MgCl2 in the heterogeneous procatalyst is from 0.005:1 to 0.25:

1.

8. The heterogeneous procatalyst of any one of the preceding claims, wherein the molar ratio of metal-ligand complex to titanium species in the heterogeneous procatalyst is from 0.1:1 to 10:

1.

9. The heterogeneous procatalyst of any one of the preceding claims, wherein the metal-ligand complex is a metal-ligand complex donor and comprises at least one of: vanadium (V) tripropoxide, vanadium (V) tributoxide, vanadium (V) triisopropoxide, titanium (IV) isopropoxide, titanium (IV) ethoxide, or combinations thereof.

10. A heterogeneous procatalyst comprising: a preformed heterogeneous procatalyst comprising: a titanium species; and a MgCl2 support; and a metal-ligand complex, wherein the metal-ligand complex comprises at least one of: vanadium (V) tripropoxide, vanadium (V) tributoxide, vanadium (V) triisopropoxide, titanium (IV) isopropoxide, or combinations thereof.

11. The heterogeneous procatalyst of any one of the preceding claims, wherein the procatalyst further comprises an additional transition metal compound.

12. The heterogeneous procatalyst of claim 11, wherein the additional transition metal compound can be independently selected from zirconium, hafnium, vanadium, and chromium.

13. The heterogeneous procatalyst of any one of the preceding claims, prepared by a process comprising heat treating a magnesium chloride at a temperature above 100 °C for a treatment time of at least 30 minutes to form the magnesium chloride component, and then contacting the magnesium chloride component with the titanium species.

14. A catalyst system for the polymerization of olefins, the catalyst system comprising: a heterogeneous procatalyst according to any one of the preceding claims; and a cocatalyst comprising an organoaluminum compound.

15. The catalyst system of claim 14, wherein the cocatalyst is selected from the group consisting of aluminum alkyls, aluminum haloalkyls, aluminum halides alkyls, and combinations thereof.

16. A polymerization process comprising contacting ethylene and optionally one or more alpha-olefin comonomers with the catalyst system of claim 14 or 15.

17. The polymerization process of claim 16, wherein the polymerization process is a solution polymerization process.

18. A catalyst system for the polymerization of olefins, the catalyst system comprising: a preformed heterogeneous procatalyst comprising: a titanium species; and a MgCl2 support; and a metal-ligand complex, wherein the metal-ligand complex comprises at least one of: vanadium (V) tripropanolate, vanadium (V) tributanolate, vanadium (V) triisopropanolate, titanium (IV) isopropanolate, or combinations thereof; and a cocatalyst comprising an organoaluminum compound.

19. The catalyst system of claim 18, wherein the cocatalyst is selected from the group consisting of aluminum alkyls, aluminum haloalkyls, aluminum halides alkyls, and combinations thereof.

20. The catalyst system of claim 18 or claim 19, wherein the molar ratio of cocatalyst to titanium species in the heterogeneous procatalyst is from 0.5: 1 to 50:

1.

21. A polymerization process comprising contacting ethylene and optionally one or more alpha-olefin comonomers with the catalyst system of any one of claims 17-20.

22. The polymerization process of claim 21, wherein the polymerization process is a solution polymerization process.

23. A method for making a heterogeneous procatalyst, the method comprising contacting a magnesium chloride component with a chlorinating agent, a titanium species, and a metal-ligand complex, wherein: said titanium species is TiCl 4-c (OR 3 ) c or TiCl 3-d (OR 3 ) d wherein R 3 is a (C1-C 20 )hydrocarbyl group, c is 0, 1, 2, 3 or 4, and d is 0, 1, 2 or 3; said magnesium chloride component is a pre-formed MgCl2 support having a specific surface area of at least 100 m 2 / g; said chlorinating agent has the structural formula Al(Cl) x (R 1 ) 3-x or Si(Cl) y (R 1 ) 4-y wherein: R 1 is (C1-C 30 )alkyl; x is 1, 2, or 3; and y is 1, 2, 3, or 4; and The metal-ligand complex has the structural formula (L) n M(Y) m (XR 2 ) b wherein: M is a metal cation; each L is a neutral ligand or (=0); each Y is halide or (Ci-C 20 )alkyl; each XR 2 is an anionic ligand, wherein X is a heteroatom or a heteroatom-containing functional group, and R 2 is a (C1-C 20 )hydrocarbyl or (C1-C 20 )heterohydrocarbyl group; n is 0, 1, or 2; m is 0, 1, 2, 3, or 4; b is 1, 2, 3, 4, 5, or 6; and the metal-ligand complex is generally charge neutral; wherein the sum of the total amount of chlorine in the chlorinating agent and the amount of OR 3 and XR 2 is in a molar ratio of 0.33 to 1.

45.

24. The method of claim 23, wherein the metal-ligand complex is in a hydrocarbon solution.

25. The method according to any one of claims 23 or 24, additionally comprising heat treating the magnesium chloride at a temperature above 100 °C for a treatment time of at least 30 minutes.

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