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WO2025128219A1 - Additif pour catalyseur - Google Patents

Additif pour catalyseur Download PDF

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Publication number
WO2025128219A1
WO2025128219A1 PCT/US2024/053204 US2024053204W WO2025128219A1 WO 2025128219 A1 WO2025128219 A1 WO 2025128219A1 US 2024053204 W US2024053204 W US 2024053204W WO 2025128219 A1 WO2025128219 A1 WO 2025128219A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
metallocene
group
activity
precatalyst
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PCT/US2024/053204
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English (en)
Inventor
Rhett A. BAILLIE
Bethany M. NEILSON
John F. Szul
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication of WO2025128219A1 publication Critical patent/WO2025128219A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • Embodiments of the present disclosure are directed towards a catalyst, more specifically, embodiments are directed towards an additive for a catalyst to produce a bimodal polymer.
  • Background Polymers may be utilized for a number of products including films and pipes, among other things. Polymers can be formed by reacting one or more types of monomers in a polymerization reaction. There was continued focus in the industry on developing new and improved materials and/or processes that may be utilized to form polymers for existing and new products. Among these polymers, bimodal high-density polyethylene (HDPE) is of great interest.
  • HDPE high-density polyethylene
  • Bimodal HDPE refers to a type of HDPE polymer that had both a high molecular weight component and a low molecular weight component, the “bimodal” molecular weight distribution.
  • a bimodal HDPE two different sets of molecular weights are present, typically achieved through a two-step polymerization process or through a combination of different polymerization conditions. This results in a polymer with a broader molecular weight distribution compared to traditional unimodal HDPE.
  • the combination of different molecular weights offer advantages, such as improved mechanical properties and processability, among others, for use in blow and rotational molded products, pipe and tubing applications along with film and packaging applications.
  • CIU cost-in-use
  • the CIU is effectively the cost of the catalyst per unit weight of the polymer produced.
  • the CIU is usually expressed in either cents-per-pound (cpp) or $/ton.
  • CIU is intimately linked to the productivity of a catalyst and becomes more economically advantageous when the productivity of the catalyst increases.
  • Catalysts for bimodal polymer production e.g., bimodal HDPE
  • the challenge in the art is to achieve improvements in the production of bimodal HDPE without changing the polymer/product produced.
  • Adjusting polymerization reaction conditions can alter catalyst productivity.
  • altering reaction conditions may have other unintended consequences.
  • altering reaction conditions can also alter various polymer properties (e.g., Mn, Mw, MWD, density, etc.), impart operability issues (e.g., agglomeration, sheeting, etc.), increase catalyst residue in the polymer, and/or increase production cost.
  • various polymer properties e.g., Mn, Mw, MWD, density, etc.
  • operability issues e.g., agglomeration, sheeting, etc.
  • increase catalyst residue in the polymer and/or increase production cost.
  • the present disclosure provides technical solutions to the above technical problems by employing an effective amount of an activity-enhancing compound, as discussed herein, to alter the molecular structure of at least a non-metallocene precatalyst in a productivity enhanced bimodal catalyst.
  • the activity-enhancing compound can be introduced during the preparation of a solid or a spray dried form of the productivity enhanced bimodal catalyst and/or a catalyst system (e.g., a multimodal catalyst system).
  • the productivity enhanced bimodal catalyst and/or a catalyst system including the productivity enhanced bimodal catalyst can be employed in a polymerization reactor to make polymers at an improved level of productivity, as detailed herein, and yet the productivity enhanced bimodal catalysts are easily and inexpensively prepared and still make polymer with desired properties (e.g., molecular weight, molecular weight distribution, etc.). This result is not predictable.
  • the present disclosure provides for changing the composition of matter for a catalyst system (e.g., a non-metallocene precatalyst and a metallocene precatalyst as provided herein) with an activity-enhancing compound to produce a productivity enhanced bimodal catalyst.
  • the results/features caused by the inclusion of the activity-enhancing compound to produce the productivity enhanced bimodal catalyst of the present disclosure include (a)-(g): (a) Increased productivity as seen by the increase in productivity of both the high molecular weight and low molecular weight components of the productivity enhanced bimodal catalyst (shown in the Examples section by the comparison of the productivity of the productivity enhanced bimodal catalyst to the comparative catalysts system that do not include the activity-enhancing compound. (b) The productivity enhanced bimodal catalyst demonstrates a higher overall productivity, whereas controls with the activity-enhancing compound and metallocene catalyst only show a decrease in productivity (e.g., the direct combination of the metallocene catalyst and the activity- enhancing compound is detrimental).
  • the activity-enhancing compound functions by chemically modifying the active high molecular weight (non-metallocene) component, which is accomplished by contacting the high molecular weight non-metallocene precatalyst with activator (e.g., methylaluminoxane, (“MAO”)) and the activity-enhancing compound in solution, slurry, or suspension in an inert hydrocarbons (other components of the bimodal catalyst system may or may not be present).
  • activator e.g., methylaluminoxane, (“MAO”)
  • MAO methylaluminoxane
  • the activity-enhancing compound has a negative impact on metallocene productivity and also no impact on the metallocene kinetics.
  • the productivity enhanced bimodal catalyst operates effectively with a decreased trim/cat ratio, which is a surprising and unpredictable feature.
  • the bimodal HDPE produced by the productivity enhanced bimodal catalyst in the semi- batch reactor method (specifically when no trim is used to adjust the ratio of LMW:HMW components) of the present disclosure has a lower Mw and Mn molecular weight from an increased LMW polymer component in the bimodal HDPE.
  • the solid catalyst system for the productivity enhanced bimodal catalyst can be comprised of the non-metallocene catalyst, the metallocene catalyst, the activity-enhancing compound, an activator and a support. Additional metallocene catalysts, as discussed herein, can also be used in the solid catalyst system of the productivity enhanced bimodal catalyst. These components can be mixed in an inert hydrocarbon solvent, as provided herein, and then spray dried to give the solid catalyst system of the productivity enhanced bimodal catalyst.
  • the effective catalyst system for the solid catalyst system of the productivity enhanced bimodal catalyst can include a slurry (e.g., mineral oil and optionally an inert hydrocarbon) of the solid (or spray dried) catalyst system of the productivity enhanced bimodal catalyst being contacted (e.g., preferably in-line to the polymerization reactor) with a trim solution of a metallocene compound, as discussed herein, in inert hydrocarbon.
  • the ratio of trim to the solid catalyst system of the productivity enhanced bimodal catalyst takes on a range and can be adjusted to make different bimodal products or to adapt to process needs.
  • FIG.1 shows internal reactor temperature profiles for Examples and Comparative Examples according to an embodiment of the disclosure.
  • FIG.2 shows internal reactor temperature profiles for Examples and Comparative Examples according to an embodiment of the disclosure.
  • FIG.3 shows internal reactor temperature profiles for Examples and Comparative Examples according to an embodiment of the disclosure.
  • FIG.4 is an ethylene uptake versus time graph for Examples and Comparative Examples according to an embodiment of the disclosure.
  • FIG.5 is an ethylene uptake versus time graph for Examples and Comparative Examples according to an embodiment of the disclosure.
  • FIG.6 is an ethylene uptake versus time graph for Examples and Comparative Examples according to an embodiment of the disclosure.
  • FIG.7 provides polymer GPC traces for Examples and Comparative Examples according to an embodiment of the disclosure. Detailed Description The entire contents of the Summary section are incorporated in the Detailed Description by reference. Additional embodiments follow; some are numbered for easy reference. Aspect 1.
  • a method of making a productivity enhanced bimodal catalyst comprising: combining a non-metallocene precatalyst, a metallocene precatalyst, an effective amount of an activator to activate the non-metallocene precatalyst and the metallocene precatalyst, and an effective amount of an activity-enhancing compound into the productivity enhanced bimodal catalyst; where the activity-enhancing compound is of Formula (A): (Formula A) where each of R 5 , R 4 and a (C 1 -C 20 )hydrocarbyl, or a (C 1 - C 20 )heterohydrocarbyl; with the proviso that at least one of R 5 and R 3 is a halogen or a haloalkyl; where each of R 2 and R 1 independently is H, a halogen, a (C 1 -C 20 )hydrocarbyl or a (C 1 - C 20 )heterohydrocarbyl,
  • Aspect 2 The method of aspect 1 where each of R 5 and R 3 is independently a halogen or haloalkyl; each of R 2 and R 1 is H; R 4 is selected from H, hydrocarbyl, halogen and haloalkyl.
  • Aspect 3 The method of aspect 1 where the activity-enhancing compound is 3,5-difluoro-1- ethynylbenzene: .
  • Aspect 4. The method of of R 5 and R 3 is halogen or haloalkyl and the other is hydrogen.
  • Aspect 5. The method of aspect 1 where the activity-enhancing compound is 3-fluoro-1- ethynylbenzene or 3,4-difluoro-1-ethynylbenzene: F F H .
  • the and R 9 independently is a (C 1 -C 5 )hydrocarbyl; each of R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 is H; M is Zr and each X is a chloro group or a (C 1 - C 3 )hydrocarbyl.
  • Aspect 7 The method of aspect 6 where R 12 is C 3 hydrocarbyl; each of R 6 , R 7 , R 8 and R 9 is a C 1 hydrocarbyl and each X is a chloro group or a methyl group.
  • Aspect 9 The method of any one the method further comprises combining the non-metallocene precatalyst, the metallocene precatalyst, the effective amount of the activator, the effective amount of the activity-enhancing compound, a support material, and an inert hydrocarbon solvent to make a mixture, and removing the inert hydrocarbon solvent from the mixture so as to give the productivity enhanced bimodal catalyst disposed on the support material.
  • Aspect 10 10.
  • non-metallocene precatalyst is a non-metallocene precatalyst of Formula (C) Formula (C) where M is a group 4 element, each of R 6 - R 13 are independently a hydrogen or a methyl group, Ar is an aryl group or a substituted aryl group, Ar’ is an aryl group or a substituted aryl group, and each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene(trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group.
  • M is a group 4 element
  • each of R 6 - R 13 are independently a hydrogen or a methyl group
  • Ar is an aryl group or a substituted aryl group
  • Ar’ is an aryl group or a substituted aryl group
  • each X is
  • AEC/NMC molar ratio activity-enhancing compound-to- non-metallocene precatalyst
  • Aspect 14 The method of any one of aspects 1 to 13, including using the metallocene precatalyst of Compound (2) : as a trim catalyst.
  • Aspect 15. A productivity made by the method of any one of aspects 1 to 14.
  • Aspect 16. A method of feeding a productivity enhanced bimodal catalyst to a slurry-phase, solution-phase, or gas-phase polymerization reactor containing an olefin monomer and a moving bed of polyolefin polymer, the method comprising making the productivity enhanced bimodal catalyst outside of the reactor and according to the method of any one of aspects 1 to 14, and feeding the productivity enhanced bimodal catalyst in neat form or as a solution or slurry thereof in an inert hydrocarbon liquid or mineral oil through a feed line free of olefin monomer into the slurry- phase, solution-phase, or gas-phase polymerization reactor.
  • Aspect 17 The method of Aspect 18 further including using the metallocene precatalyst of Compound (2): as a trim catalyst with the productivity enhanced bimodal catalyst of any of claims 1-10 in a slurry- phase, solution-phase, or gas-phase polymerization reactor.
  • Aspect 18 The catalyst of the method of any of claims 16 to 17 such that the productivity enhanced bimodal catalyst has a decreased trim requirement compared to the bimodal without an activity enhancing compound, which can be measured in a continuous process by a decreased amount of trim in moles relative to the base catalyst, or an increased activity in lb PE/mol of the low molecular weight metallocene catalyst, which is accompanied by an increase in activity in lb PE/mol of the high molecular weight non-metallocene catalysts.
  • the increase in activity may be from 5% to 100%, or from 5% to 50%, or from 10% to 90%, or from 10% to 50%, or from 20% to 40%, or from 10% to 25%.
  • Aspect 19 The method of any one of claims 17 to 19 further including using a continuity additive with the productivity enhanced bimodal catalyst in the slurry-phase, solution-phase, or gas- phase polymerization reactor.
  • Aspect 20 The method of any one of claims 17 to 19 further including using a continuity additive with the productivity enhanced bimodal catalyst in the slurry-phase, solution-phase, or gas- phase polymerization reactor.
  • Aspect 21 The method of Aspect 20 where the continuity additive is CA-300.
  • Aspect 22 A multimodal catalyst system comprising the productivity enhanced bimodal catalyst made by the method of any one of Aspects 1 to 16, and at least one second catalyst selected from a different metallocene catalyst and a different non-metallocene catalyst.
  • Aspect 23 A method of making a polyolefin polymer, the method comprising contacting at least one 1-alkene monomer with the productivity enhanced bimodal catalyst made by the method of any one of aspects 1 to 16, or the multimodal catalyst system of aspect 22, in a slurry-phase, solution-phase, or gas-phase polymerization reactor under polymerizing conditions, thereby making the polyolefin polymer.
  • Aspect 24 Aspect 24.
  • Aspect 25. A manufactured article made from the polyolefin polymer of aspect 24.
  • Aspect 26. The method of Aspect 19, where the high molecular weight (HMW) catalyst component, i.e., the non-metallocene catalyst component, has an increased activity (given in lb PE/mol HMW catalyst) of >20%.
  • Aspect 27. The method of Aspect 19, where the high molecular weight (HMW) catalyst component, i.e., the non-metallocene catalyst component, has an increased activity (given in lb PE/mol HMW catalyst) of >20%.
  • Aspect 30 The method of Aspects 19 to 29, where the LMW catalyst component, i.e., the metallocene catalyst component, has an increased activity (given in lb PE/mol HMW catalyst) of >50%.
  • Aspect 32 The method of any one of Aspects 26 to 30, where the activities given in pounds polyethylene per mole of molecular catalyst component of both the HMW (i.e., non-metallocene) and LMW (i.e., metallocene) catalyst components have increased by >20%.
  • Aspect 32 The method of any one of Aspects 26 to 31, where the activities given in pounds polyethylene per mole of molecular catalyst component of both the HMW (i.e., non-metallocene) and LMW (i.e., metallocene) catalyst components have increased by >40%.
  • Aspect 33 The method of any one of Aspects 26 to 30, where the activities given in pounds polyethylene per mole of molecular catalyst component of both the HMW (i.e., non-metallocene) and LMW (i.e., metallocene) catalyst components have increased by >40%.
  • Aspect 19 where a ratio of the trim catalyst to dry catalyst is decreased compared to a bimodal catalyst without the activity-enhancing compound to produce the same polymer and given that the concentrations of a feed of the trim catalyst and the feed of the bimodal catalyst are equivalent.
  • Aspect 34 The method of Aspect 19, where less trim catalyst measured in terms of moles of trim catalyst or grams of trim catalyst are required to make the same polymer with the productivity enhanced bimodal catalyst compared to the bimodal catalyst without the activity- enhancing compound.
  • Aspect 35 The method of any one of Aspects 19 to 34, where the productivity enhanced bimodal catalyst has an increased catalyst lifetime as shown by having an increased HMW catalyst activity of >50% when the residence time is >4 hours compared to the bimodal catalyst without the activity-enhancing compound.
  • Aspect 36 The method of any one of Aspects 19 to 34, where the productivity enhanced bimodal catalyst has an increased catalyst lifetime as shown by having an increased HMW catalyst activity of >50% when the residence time is >4 hours compared to the bimodal catalyst without the activity-enhancing compound.
  • Aspect 37 The method of any one of Aspects 19 to 34, where the productivity enhanced bimodal catalyst has an increased catalyst lifetime as shown by having an increased HMW catalyst activity of >50% and an increased LMW catalyst activity of >50% when the residence time is >4 hours compared to the bimodal catalyst without the activity-enhancing compound.
  • Aspect 37 The method of any one of Aspects 19 to 34, where the productivity enhanced bimodal catalyst has a higher or equal productivity than the bimodal catalyst without the activity- enhancing compound under conditions where the amount of induced condensing agent (ICA) is decreased by more than 50%.
  • Aspect 38 The method of Aspect 37, where the induced condensing agent is isopentane.
  • Aspect 39 The method of Aspect 38, where the isopentane feed is ⁇ 10 mol%.
  • Aspect 40 The method of Aspect 38, where the isopentane feed is ⁇ 5 mol%.
  • Aspect 48 The method of any one of Aspects 1-47, where the bimodal catalyst containing the activity-enhancing compound of Formula (A) has a longer catalyst lifetime than the same bimodal catalyst that does not containing activity-enhancing compound of formula (A).
  • the method of making a productivity enhanced bimodal catalyst comprises combining in any order constituents consisting essentially of a non- metallocene precatalyst, a metallocene precatalyst, an effective amount of an activator, and an effective amount of an activity-enhancing compound under conditions effective for the activator and the activity-enhancing compound to activate the non-metallocene precatalyst and the metallocene precatalyst into the productivity enhanced bimodal catalyst, thereby making the productivity enhanced bimodal catalyst.
  • the activity-enhancing compound may be of Formula (A), as detailed herein.
  • the metallocene precatalyst may be a metallocene precatalyst of Formula (B), as detailed herein.
  • the non-metallocene precatalyst may be a non-metallocene precatalyst of Formula (C), as detailed herein.
  • metal M for either the metallocene precatalyst of Formula (B) and/or the non-metallocene precatalyst of Formula (C) is Zr or Hf; alternatively M is Zr or Ti; alternatively M is Ti or Hf; alternatively M is Zr; alternatively M is Hf; alternatively M is Ti.
  • Embodiments of the method of making may comprise any one of synthesis schemes 1 to 15.
  • Synthesis Scheme 1 Step (a) non-metallocene precatalyst + metallocene precatalyst + excess activator ⁇ intermediate mixture of activated non-metallocene catalyst + activated metallocene + leftover activator. Step (b) intermediate mixture + effective amount of activity-enhancing compound ⁇ productivity enhanced bimodal catalyst + the leftover activator.
  • Synthesis Scheme 2 Step (a) + non-metallocene precatalyst + metallocene precatalyst + effective amount of activity-enhancing compound ⁇ intermediate non-metallocene precatalyst + intermediate metallocene precatalyst (unreacted mixture or reaction product of non-metallocene precatalyst + metallocene precatalyst + activity-enhancing compound).
  • Step (b) intermediate non- metallocene precatalyst + intermediate metallocene precatalyst + activator e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)
  • Synthesis Scheme 3 Step (a) non-metallocene precatalyst + metallocene precatalyst + activator (e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)) ⁇ activated non- metallocene catalyst + activated metallocene catalyst. Step (b) activated non-metallocene catalyst + activated metallocene catalyst + effective amount of activity-enhancing compound ⁇ productivity enhanced bimodal catalyst.
  • Step (a) activator e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)
  • activator e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)
  • Step (b) Intermediate mixture + non-metallocene precatalyst + metallocene precatalyst ⁇ productivity enhanced bimodal catalyst.
  • Synthesis Scheme 5 Step (a) activator ⁇ non-metallocene precatalyst + metallocene precatalyst ⁇ effective amount of activity- compound (simultaneous but separate additions of activator and activity-enhancing compound to non-metallocene precatalyst + metallocene precatalyst) ⁇ productivity enhanced bimodal catalyst. Step (b): none.
  • step (a) further includes an inert hydrocarbon solvent and deposition on the support material is performed by evaporating the solvent, alternatively by spray-drying.
  • Synthesis Scheme 7 Step (a) non-metallocene precatalyst + excess activator (e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)) ⁇ intermediate mixture of activated non- metallocene catalyst + leftover activator.
  • step (b) intermediate mixture + effective amount of activity-enhancing compound ⁇ intermediate mixture of reaction product of activity-enhancing compound and activated + excess activity-enhancing compound.
  • Synthesis scheme 7 can be practiced with or without a support as provided herein.
  • Synthesis Scheme 8 Step (a) non-metallocene precatalyst + excess activator (e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)) + support material ⁇ intermediate mixture of activated non-metallocene catalyst + leftover activator + support
  • Step (b) intermediate mixture + effective amount of activity-enhancing compound ⁇ intermediate mixture of reaction product of activity-enhancing compound and activated non-metallocene + excess activity-enhancing compound + support material.
  • step (a) further includes an inert hydrocarbon solvent and deposition on the support material is performed by evaporating the solvent, alternatively by spray-drying.
  • the amount of activator may be a stoichiometric amount relative to the metal M of the non- metallocene catalyst (e.g., a molar ratio of 1.0 to 1.0); alternatively a less than stoichiometric amount relative thereto (e.g., a molar ratio of from 0.1 to 0.94); alternatively an excess amount (e.g., a molar ratio from 1.1 to 10,000) relative thereto; alternatively the metal of the non- metallocene precatalyst, M, where the activator is an organoaluminum compound, as provided herein, and where the effective amount of the activator is an Al/M molar ratio of from 0.5 to 10,000, alternatively from 0.95 to 200, alternatively from 1.0 to 150, alternatively from 10 to 100; and/or where the effective amount of the activity-enhancing
  • the support material examples are alumina and hydrophobized fumed silica; alternatively the hydrophobized fumed silica.
  • the hydrophobized fumed silica may be made by surface-treating an untreated, anhydrous fumed silica with an effective amount of a hydrophobing agent.
  • the hydrophobing agent may be dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane; alternatively dimethyldichlorosilane.
  • the hydrophobized fumed silica made by surface-treating an untreated, anhydrous fumed silica with dimethyldichlorosilane may be CABOSIL® TS-610, which is a fumed silica that is surface treated with dimethyldichlorosilane.
  • Synthesis Scheme 9 Step (a) non-metallocene precatalyst + metallocene precatalyst + effective amount of activity-enhancing compound + support material ⁇ intermediate mixture of non- metallocene precatalyst + metallocene precatalyst and activity-enhancing compound disposed on (or in equilibrium with) support material.
  • Step (b) intermediate mixture + activator (e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)) ⁇ productivity enhanced bimodal catalyst disposed on (or in equilibrium with) support material.
  • step (a) further includes an inert hydrocarbon solvent and deposition on the support material is performed by evaporating the solvent, alternatively by spray-drying.
  • activator e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)
  • step (a) further includes an inert hydrocarbon solvent and deposition on the support material is performed by evaporating the solvent, alternatively by spray-drying.
  • Step (a) activator e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)
  • activator e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)
  • MAO methylaluminoxane
  • Step (b) Intermediate solution + non-metallocene precatalyst + precatalyst + support material ⁇ productivity enhanced bimodal catalyst disposed on (or in equilibrium with) support material.
  • step (b) further includes an inert hydrocarbon solvent and deposition on the support material is performed by evaporating the solvent, alternatively by spray- drying.
  • Step (a) activator ⁇ non-metallocene precatalyst + metallocene precatalyst + support material ⁇ effective of activity-enhancing compound (simultaneous but separate additions of activator and activity-enhancing compound to mixture of non-metallocene precatalyst + metallocene precatalyst + support material) ⁇ productivity enhanced bimodal catalyst disposed on (or in equilibrium with) support material.
  • Step (b) none.
  • step (a) further includes an inert hydrocarbon solvent and deposition on the support material is performed by evaporating the solvent, alternatively by spray-drying.
  • Step (e) may be performed by conventional evaporating of the inert hydrocarbon solvent from the suspension from step (d) or by spray-drying the suspension from step (d).
  • Synthesis Scheme 14 Step (a): activator (e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)) + support material (e.g., hydrophobic fumed silica) + inert hydrocarbon solvent ⁇ slurry of supported excess activator disposed on (or in equilibrium with) support material in inert hydrocarbon solvent.
  • activator e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)
  • support material e.g., hydrophobic fumed silica
  • Step (d) to slurry of Step (c) with + metallocene precatalyst ⁇ slurry of supported productivity enhanced bimodal catalyst disposed on (or in equilibrium with) the support material and supported excess activator disposed on (or in equilibrium with) support material in inert hydrocarbon solvent.
  • Step (e) may be performed by conventional evaporating of the inert hydrocarbon solvent from the suspension from step (d) or by spray-drying the suspension from step (d).
  • Synthesis Scheme 15 Making a multimodal catalyst system comprising the productivity enhanced bimodal catalyst and a different catalyst (e.g., a metallocene catalyst) spray-dried on a silica support: Step (a) non-metallocene precatalyst + metallocene precatalyst + support material + activator (e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)) ⁇ activated non- metallocene catalyst + activated metallocene catalyst disposed on (or in equilibrium with) support material.
  • activator e.g., an alkylaluminoxane such as methylaluminoxane (“MAO”)
  • step (a) further includes an inert hydrocarbon solvent and deposition on the support material is performed by evaporating the solvent, alternatively by spray-drying.
  • slurry support material e.g., fumed silica
  • MAO a solvent
  • non- metallocene precatalyst e.g., toluene
  • a solvent e.g., toluene
  • non- metallocene precatalyst e.g., toluene
  • activity-enhancing compound e.g., 1 hour
  • second different precatalyst e.g., a metallocene precatalyst
  • the multimodal catalyst system may be fed into the gas-phase polymerization reactor.
  • an additional quantity of the productivity enhanced bimodal catalyst or an additional quantity of the second precatalyst may be separately fed into the reactor as a solution thereof in an inert hydrocarbon solvent, where it contacts the multimodal catalyst system.
  • a separate catalyst and/or precatalyst solution is sometimes called a trim catalyst.
  • the multimodal catalyst system may be contacted with a feed of the trim catalyst in a feed line heading into the reactor.
  • the multimodal catalyst system such as a trimodal catalyst system may be made in situ in a gas-phase polymerization reactor by adding the productivity enhanced bimodal catalyst and at least one second catalyst and/or precatalyst separately into the reactor, where they contact each other, thereby making the multimodal catalyst system in situ in the reactor.
  • the method of any one of the above aspects may further comprise a step of transferring polymer granules, made in the gas-phase, solution-phase, or slurry-phase polymerization reactor and containing in the granules fully-active productivity enhanced bimodal catalyst, into a (second) gas phase polymerization reactor.
  • Activity-Enhancing Compound may be of Formula (A), as detailed herein.
  • the activity-enhancing compound of Formula (A) surprisingly and beneficially improves productivity, and does not function as a poison to the non-metallocene catalyst (or may at most function mildly as such) as may have been perceived be a skilled person viewing the organic compound of Formula (A) in the absence of Applicant’s surprising discovery herein.
  • the compound of Formula (A) is an alkyne.
  • each of R 5 and R 3 in Formula A can be a halogen or haloalkyl.
  • each of R 2 and R 1 can be H.
  • R 4 can be H.
  • the activity-enhancing compound can be 3,5-difluoro-1-ethynylbenzene.
  • each of R 3 and R 4 in Formula A can be a halogen or haloalkyl.
  • each of R 5 , R 2 and R 1 can be H.
  • the activity-enhancing compound can be 3,4-difluoro-1-ethynylbenzene.
  • R 3 in Formula A can be a halogen or haloalkyl.
  • each of R 5 , R 4 , R 2 and R 1 can be H.
  • the activity-enhancing compound can be 3- fluoro-1-ethynylbenzene.
  • each of R 3 , R 4 , and R 5 in Formula A can be a halogen or haloalkyl.
  • each of R 2 and R 1 can be H.
  • the activity-enhancing compound can be 3,4,5-trifluoro-1-ethynylbenzene. Metallocene Precatalyst.
  • the metallocene precatalyst can be combined with the non-metallocene precatalyst, the effective amount of the activator, and the effective amount of the activity-enhancing compound to activate the metallocene precatalyst and the non- metallocene precatalyst into the productivity enhanced bimodal catalyst.
  • the metallocene precatalyst is a metallocene precatalyst of Formula (B): Formula (B) where M is a Group 4 a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene(trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group; each of R 6 and R 9 independently is a (C 1 - C 5 )hydrocarbyl; each of R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 is H; M is Zr and each X is a chloro group or a (C 1 - C 3 )hydrocarbyl.
  • M is a Group 4 a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a flu
  • each of R 6 and R 9 is a C 1 hydrocarbyl and each X is a chloro group or a methyl group.
  • Specific examples of the metallocene precatalyst of Formula (B) include those of compound (1) and compound (2): Non-metallocene Precatalyst.
  • the non-metallocene precatalyst can be combined with the metallocene precatalyst, the effective amount of the activator, and the effective amount of an activity-enhancing compound to activate the non-metallocene precatalyst and the metallocene precatalyst into the productivity enhanced bimodal catalyst.
  • the non-metallocene precatalyst is a non-metallocene precatalyst of formula (C) Formula (C) where M is a group 4 a hydrogen or a methyl group, Ar is an aryl group or a substituted aryl group, Ar’ is an aryl group or a substituted aryl group, and each X is, independently, a hydride group, an amide, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene(trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group.
  • each X is independently a silicon-containing alkyl.
  • each X is independently a tri-hydrocarbylsilylmethyl.
  • each X is independently a methylene(trimethylsilyl) group.
  • at least one X is ((C 1 -C 20 )alkyl) 3-g -(phenyl) g Si- where subscript g is 0, 1, 2, or 3; alternatively, where subscript g is 0 or 1; alternatively 0; alternatively 1.
  • at least one X is a (C 6 -C 12 )aryl-((C 0 -C 10 )alkylene)-CH 2 (e.g., benzyl).
  • each X is independently a (C 6 -C 12 )aryl-((C 0 -C 10 )alkylene)-CH 2 , alternatively one X is a (C 6 -C 12 )aryl-((C 0 -C 10 )alkylene)- CH 2 (e.g., benzyl) and the other X is F, Cl, or methyl; alternatively each X is benzyl.
  • each X is benzyl, alternatively one X is a benzyl and the other X is F, Cl, or methyl.
  • each X is a (C 1 -C 6 )alkoxy-substituted (C 6 -C 12 )aryl or a (C 1 -C 6 )alkoxy-substituted benzyl.
  • the activated non-metallocene catalyst is a non-metallocene catalyst for the formula (C-I) I); where each of the gro d for formula (C); where A- is an ion (used to formally balance the positive charge of the metal M).
  • the ligand in the non-metallocene catalyst that is derived from the activity-enhancing compound may be a group R (“ligand R”).
  • the (C 1 -C 20 )hydrocarbyl may be unsubstituted and consist of carbon atoms and hydrogen atoms or the (C 1 -C 20 )hydrocarbyl may be substituted and consist of carbon, hydrogen, and one or more halogen atoms.
  • Each halogen atom is independently selected from F, Cl, Br, and I; alternatively from F, Cl, and Br; alternatively from F and Cl; alternatively from F; alternatively from Cl.
  • the unsubstituted (C 1 -C 20 )hydrocarbyl may be an unsubstituted (C 1 - C 20 )alkyl, an unsubstituted (C 3 -C 20 )cycloalkyl, an unsubstituted (C 6 -C 12 )aryl, an unsubstituted ((C 1 -C 4 )alkyl) 1-3 -phenyl, or an unsubstituted (C 6 -C 12 )aryl-(C 1 -C 6 )alkyl.
  • the substituted (C 1 - C 20 )hydrocarbyl may be a monofluoro or difluoro derivative of the aforementioned unsubstituted (C 1 -C 20 )hydrocarbyl, such as 2-(3,4-difluorophenyl)-ethen-1-yl (of formula (A)).
  • Each (C 1 -C 19 )heterohydrocarbyl, of embodiments of R 14 to R 16 containing the same, may be unsubstituted and consist of carbon atoms, hydrogen atoms, and at least one heteroatom selected from N and O or the (C 1 -C 17 )heterohydrocarbyl may be substituted and consist of carbon atoms, hydrogen atoms, at least one heteroatom selected from N and O, and one or more halogen atoms.
  • the unsubstituted (C 1 -C 17 )heterohydrocarbyl may be (C 1 -C 19 )heteroalkyl, (C 3 - C 19 )heterocycloalkyl, (C 6 -C 12 )heteroaryl, ((C 1 -C 4 )alkoxy) 1-3 -phenyl, or (C 6 -C 12 )heteroaryl-(C 1 - C 6 )alkyl.
  • the substituted (C 1 -C 17 )heterohydrocarbyl may be a monofluoro or difluoro derivative of the aforementioned unsubstituted (C 1 -C 17 )heterohydrocarbyl, such as 2-(3,5-difluorophenyl)- ethen-1-yl (of formula (A)).
  • the (C 1 -C 20 )hydrocarbyl may be unsubstituted and consist of carbon atoms and hydrogen atoms or the (C 1 -C 20 )hydrocarbyl may be substituted and consist of carbon, hydrogen, and one or more halogen atoms.
  • Each halogen atom is independently selected from F, Cl, Br, and I; alternatively from F, Cl, and Br; alternatively from F and Cl; alternatively from F; alternatively from Cl.
  • the unsubstituted (C 1 -C 20 )hydrocarbyl may be an unsubstituted (C 1 -C 20 )alkyl, an unsubstituted (C 3 -C 20 )cycloalkyl, an unsubstituted (C 6 -C 12 )aryl, an unsubstituted ((C 1 -C 4 )alkyl) 1-3 -phenyl, or an unsubstituted (C 6 -C 12 )aryl-(C 1 -C 6 )alkyl.
  • the substituted (C 1 -C 20 )hydrocarbyl may be a monofluoro or difluoro derivative of the aforementioned unsubstituted (C 1 -C 20 )hydrocarbyl, such as 2-(3,5- difluorophenyl)-ethen-1-yl (of formula (A)).
  • the non-metallocene catalyst with ligand R derived from the additive catalyst may be given by either or both of formula (C-III) and (C-IV):
  • the first non-metallocene precatalyst of Formula (C) can be of compound (3),
  • each X is, independently, a hydride enzyl group, a methyl group, a chloro group, a fluoro group, a methylene(trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group.
  • each X is independently a silicon- containing alkyl.
  • each X is independently a tri- hydrocarbylsilylmethyl.
  • each X is independently a methylene(trimethylsilyl) group.
  • the first non-metallocene precatalyst of Formula (C) can be compound (1), and each X can be a benzyl group.
  • the non-metallocene precatalyst of Formula (C) can be of compound (4): .
  • the various catalyst with a ligand derived from the activity- enhancing compound can be of either or both of compound (4-A) and compound (4-B):
  • AEC Activity-Enhancing Compound
  • a quantity of activity- enhancing compound (AEC) is sufficient to make a productivity enhanced bimodal catalyst.
  • the effective amount of AEC may be expressed in absolute terms compared to the amount of (pre)catalyst metal M or in relative terms compared to the productivity performance or as a combination thereof.
  • the effective amount of the activity-enhancing compound may be expressed as a molar ratio of moles of activity-enhancing compound to moles of metal M (“MAEC mol /M mol ”), where M is the M of the non-metallocene precatalyst of structural Formula (C), e.g., M is a Group 4 metal.
  • the effective amount of the AEC is expressed as a PAEC mol /M mol of ⁇ 0.50/1.0, alternatively ⁇ 0.9/1.0; alternatively ⁇ 1.0/1.0; alternatively ⁇ 1.5/1.0; alternatively ⁇ 1.9/1.0; alternatively ⁇ 3/1.0; alternatively ⁇ 5/1.0; alternatively ⁇ 6/1.0; alternatively ⁇ 9/1.0; alternatively ⁇ 10.0/1.0, alternatively ⁇ 10.0/1.0, alternatively ⁇ 20.0/1.0, alternatively ⁇ 30.0/1.0, alternatively ⁇ 40.0/1.0, alternatively ⁇ 50.0/1.0.
  • the immediately foregoing embodiments may be described by expressing the effective amount of the AEC as an inverse molar ratio of moles of metal M to moles of activity-enhancing compound (“M mol /MAC mol ”) as follows: ⁇ 1.0/0.5; alternatively ⁇ 1.0/0.9; alternatively ⁇ 1.0/1.0; alternatively ⁇ 1.0/1.5; alternatively ⁇ 1.0/1.9; alternatively ⁇ 1.0/3.0; alternatively ⁇ 1.0/5.0; alternatively ⁇ 1.0/6.0; alternatively ⁇ 1.0/9.0; alternatively ⁇ 1.0/10.0, alternatively ⁇ 1.0/20.0, alternatively ⁇ 1.0/30.0, alternatively ⁇ 1.0/40.0, alternatively ⁇ 1.0/50.0, respectively.
  • the MAC mol /M mol is limited to at most 40/1; alternatively at most 30/1; alternatively at most 20/1; alternatively at most 10.0; alternatively at most 6.0; alternatively at most 5.0; alternatively at most 1.5.
  • the effective amount of the activity-enhancing compound (AEC) may provide a productivity enhanced bimodal catalyst having improved productivity.
  • the productivity enhanced bimodal catalyst and the effective amount of the AEC is characterized by having improved productivity.
  • the productivity enhanced bimodal catalyst is made from any one of the non-metallocene precatalyst of Formula (C) such as compounds (1), described herein. Continuity Additive/Static Control Agent.
  • a static control agent is a chemical composition which, when introduced into a fluidized bed reactor, may influence or drive the static charge (negatively, positively, or to zero) in the fluidized bed.
  • the specific static control agent used may depend upon the nature of the static charge, and the choice of static control agent may vary dependent upon the polymer being produced and the single site catalyst compounds being used.
  • the use of static control agents is disclosed in European Patent No. 0229368 and U.S. Pat. Nos.4,803,251; 4,555,370; and 5,283,278, and references cited therein.
  • Control agents such as aluminum stearate may be employed.
  • the static control agent used may be selected for its ability to receive the static charge in the fluidized bed without adversely affecting productivity.
  • Other suitable static control agents may also include aluminum distearate, ethoxlated amines, and anti-static compositions such as those provided by Innospec Inc. under the trade name OCTASTAT.
  • OCTASTAT 2000 is a mixture of a polysulfone copolymer, a polymeric polyamine, and oil-soluble sulfonic acid.
  • any of the aforementioned control agents, as well as those described in, for example, WO 01/44322, listed under the heading Carboxylate Metal Salt and including those chemicals and compositions listed as antistatic agents may be employed either alone or in combination as a control agent.
  • the carboxylate metal salt may be combined with an amine containing control agent (e.g., a carboxylate metal salt with any family member belonging to the KEMAMINE® (available from Crompton Corporation) or ATMER® (available from ICI Americas Inc.) family of products).
  • Other useful continuity additives include ethyleneimine additives useful in embodiments disclosed herein may include polyethyleneimines having the following general formula: (CH 2 —CH 2 —NH) n — in which n may be from about 10 to about 10,000.
  • the polyethyleneimines may be linear, branched, or hyperbranched (e.g., forming dendritic or arborescent polymer structures). They can be a homopolymer or copolymer of ethyleneimine or mixtures thereof (referred to as polyethyleneimines hereafter). Although linear polymers represented by the chemical formula —[CH 2 —CH 2 —NH]— may be used as the polyethyleneimine, materials having primary, secondary, and tertiary branches can also be used. Commercial polyethyleneimine can be a compound having branches of the ethyleneimine polymer. Suitable polyethyleneimines are commercially available from BASF Corporation under the trade name Lupasol. These compounds can be prepared as a wide range of molecular weights and product activities.
  • Examples of commercial polyethyleneimines sold by BASF suitable for use in the present invention include, but are not limited to, Lupasol FG and Lupasol WF.
  • Another useful continuity additive can include a mixture of aluminum distearate and an ethoxylated amine-type compound, e.g., IRGASTAT AS-990, available from Huntsman (formerly Ciba Specialty Chemicals).
  • Other commercial examples of continuity additives include UT-CA-300 (Univation Technologies, LLC), which is a mixture of aluminum distearate and an ethoxylated amine type compound.
  • the mixture of aluminum distearate and ethoxylated amine type compound can be slurried in mineral oil e.g., Hydrobrite 380.
  • the mixture of aluminum distearate and an ethoxylated amine type compound can be slurried in mineral oil to have total slurry concentration of ranging from about 5 wt. % to about 50 wt. % or about 10 wt. % to about 40 wt. %, or about 15 wt. % to about 30 wt. %.
  • Other useful static control agents and additives are disclosed in U.S. Patent Application Publication No.2008/0045663.
  • the continuity additives or static control agents may be added to the reactor in an amount ranging from 0.05 to 200 ppm, based on ethylene feed rate or polymer production rate.
  • the continuity additive may be added in an amount ranging from 2 to 100 ppm, or in an amount ranging from 4 to 50 ppm.
  • Catalyst productivity of the catalysts provided herein (e.g., the productivity enhanced bimodal catalyst) is determined to be the catalyst’s polymerization productivity, expressed as number of pounds dried polyolefin product made per pound of dry bimodal catalyst added (lbPE/lbcat), or alternatively expressed as number of grams dried polyolefin product made per gram of bimodal catalyst added (gPE/gcat).
  • Catalyst activity may be used interchangeably with catalyst productivity. Catalyst activity.
  • Catalyst activity of a bimodal catalyst is determined to be the bimodal catalyst’s polymerization productivity, expressed as the number of pounds dried polyolefin product in terms made per mole of molecular catalyst component.
  • the catalyst activity may be expressed in terms of both molecular catalyst components of the bimodal catalyst or just one individual molecular catalyst component of the bimodal catalyst, e.g. the activity of the HMW catalyst component or the activity of the non-metallocene catalyst component. Catalyst structures.
  • the molecular structure of a non-metallocene catalyst formed from the non-metallocene precatalyst of Formula (C)
  • the molecular structure of a metallocene precatalyst formed from the metallocene precatalyst of Formula (B)
  • the molecular structure of the productivity enhanced bimodal catalyst may be determined by conventional analytical methods such as nuclear magnetic resonance (NMR) spectroscopy or gas chromatography/mass spectrometry (GC/MS).
  • Activating step In some embodiments the method of making productivity enhanced bimodal catalyst further comprises the activating step as a preliminary step, which may be completed before start of the combining step.
  • the activating step comprises contacting the non- metallocene precatalyst of Formula (C) and the metallocene precatalyst of Formula (B) with the activator under the effective activating conditions; contacting with the activity-enhancing compound of Formula (A) makes the productivity enhanced bimodal catalyst.
  • the activating step may be done in various orders, such as by contacting the non-metallocene precatalyst of Formula (C) with the activator under the effective activating conditions and then adding activity-enhancing compound of Formula (A), and then adding the metallocene precatalyst of Formula (B) to the above.
  • the activating step may be performed in the absence of the activity-enhancing compound. Activator.
  • the activator for activating the metallocene precatalyst of Formula (B) and the non-metallocene precatalyst of Formula (C) may be an alkylaluminoxane, an organoborane compound, an organoborate compound, or a trialkylaluminum compound.
  • the activator may also be a combination of any two or more thereof.
  • the activator may comprise an alkylaluminoxane and an organoborate compound such as a methylaluminoxane and an organoborate having CAS name Amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (Amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)).
  • Alkylaluminoxane also referred to as alkylalumoxane. A product of a partial hydrolysis of a trialkylaluminum compound.
  • Embodiments may be a (C 1 -C 10 )alkylaluminoxane, alternatively a (C 1 -C 6 )alkylaluminoxane, alternatively a (C 1 -C 4 )alkylaluminoxane, alternatively a (C 1 - C 3 )alkylaluminoxane, alternatively a (C 1 -C 2 )alkylaluminoxane, alternatively a methylaluminoxane (MAO), alternatively a modified-methylaluminoxane (MMAO).
  • the alkylaluminoxane is a MAO.
  • the alkylaluminoxane is supported on untreated silica, such as fumed silica.
  • the alkylaluminoxane may be obtained from a commercial supplier or prepared by any suitable method. Suitable methods for preparing alkylaluminoxanes are well- known. Examples of such preparation methods are described in U.S. Pat.
  • the maximum amount of alkylalumoxane may be selected to be a 5,000-fold molar excess over the precatalysts based on the molar ratio of moles of Al metal atoms in the aluminoxane to moles of metal atoms M (e.g., Ti, Zr, or Hf) in the precatalysts.
  • the minimum amount of activator-to- precatalyst may be a 1:1 molar ratio (Al/M).
  • the maximum may be a molar ratio of Al/M of 150, alternatively 124.
  • the organoborane compound may be selected to be a 5,000-fold molar excess over the precatalysts based on the molar ratio of moles of Al metal atoms in the aluminoxane to moles of metal atoms M (e.g., Ti, Zr, or Hf) in the precatalysts.
  • a tri(fluoro-functional organo)borane compound such as tris(pentafluorophenyl)borane ((C 6 F 5 ) 3 B), tris[3,5-bis(trifluoromethyl)phenyl] borane ((3,5-(CF 3 ) 2 -C 6 H 3 ) 3 B), or a mixture of any two or more thereof.
  • the organoborate compound such as tris(pentafluorophenyl)borane ((C 6 F 5 ) 3 B), tris[3,5-bis(trifluoromethyl)phenyl] borane ((3,5-(CF 3 ) 2 -C 6 H 3 ) 3 B), or a mixture of any two or more thereof.
  • the organoborate compound such as tris(pentafluorophenyl)borane ((C 6 F 5 ) 3 B), tris[3,5-bis(trifluoromethyl)phenyl] borane ((3,5-(CF
  • a tetra(fluoro-functional organo)borate compound((fluoro- organo) 4 B) such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate, or triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or a mixture of any two or more thereof.
  • the organoborate compound may be a methyldi((C 14 -C 18 )alkyl)ammonium salt of tetrakis(pentafluorophenyl)borate, which may be obtained from Boulder Scientific or prepared by reaction of a long chain trialkylamine (ArmeenTM M2HT, available from Akzo-Nobel, Inc.) with HCl and Li[B(C 6 F 5 ) 4 ]. Such a preparation is disclosed in US 5,919,983, Ex.2.
  • the organoborate compound may be used herein without (further) purification.
  • examples include amines, bis(hydrogenated tallow alkyl)methyl, and tetrakis(pentafluorophenyl)borate.
  • Trialkylaluminum compounds may be utilized as activators for precatalysts or as scavengers to remove residual water from polymerization reactor prior to start-up thereof.
  • suitable alkylaluminum compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n- hexylaluminum, and tri-n-octylaluminum.
  • the activator also known as a cocatalyst, may affect the molecular weight, degree of branching, comonomer content, or other properties of the polyolefin polymer.
  • the activator may enable coordination polymerization or cationic polymerization.
  • the choice of activator used to activate the non-metallocene precatalyst and/or the metallocene precatalyst does not influence the structure of the productivity enhanced bimodal catalyst made from the non-metallocene precatalyst and the metallocene precatalyst. That is, the structures of the productivity enhanced bimodal catalyst made using different activators are expected to be identical. Effective conditions.
  • the reactions described herein e.g., the combining step, the activating step, the polymerization independently are conducted under circumstances that allow the activation/reaction to proceed.
  • Examples of effective conditions are reaction temperature, type of atmosphere (e.g., inert atmosphere), purity of reactants, stoichiometry of reactants, agitation/mixing of reactants, and reaction time period.
  • Conditions effective for activating and polymerizing steps may be those described in the art and well-known to the ordinary skilled person.
  • activating effective conditions may comprise techniques for manipulating catalysts such as in-line mixers, catalyst preparation reactors, and polymerization reactors.
  • the activation temperature may be from 0 o to 800 oC, alternatively from 20 o to 50 oC.
  • the activation time may be from 10 seconds to 2 hours. Examples of gas-phase polymerizing conditions are described later herein.
  • Effective conditions for the combining step used to make the productivity enhanced bimodal catalyst may comprise a reaction temperature from -50 ° to 80 °C, alternatively from 0 ° to 50 °C, alternatively from -50 ° to 50 °C, alternatively from -50 ° to 30 °C, an inert atmosphere (e.g., nitrogen, helium, or argon gas free of water and O 2 ), reactants that are free of water and O 2 and having a purity from 90% to 100%, amounts of reactants for minimizing waste/maximizing product yield, stirring or mixing reactants, and a reaction time period from 1 minute to 24 hours.
  • Effective reaction conditions for making the productivity enhanced bimodal catalyst may comprise a reaction temperature from -50 ° to 80 °C, alternatively from 0 ° to 50 °C, alternatively from -50 ° to 50 °C, alternatively from -50 ° to 30 °C, an inert atmosphere (e.g., nitrogen, helium, or argon gas free of water and O 2 ), react
  • Such conditions may comprise techniques for manipulating air-sensitive and/or moisture-sensitive reagents and reactants such as Schlenk-line techniques and an inert gas atmosphere (e.g., nitrogen, helium, or argon).
  • Effective reaction conditions may also comprise a sufficient reaction time, a sufficient reaction temperature, and a sufficient reaction pressure.
  • Each reaction temperature independently may be from -78 o to 120 oC, alternatively from -30 o to 30 oC.
  • Each reaction pressure independently may be from 95 to 105 kPa, alternatively from 99 to 103 kPa.
  • Progress of any particular reaction step may be monitored by analytical methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry to determine a reaction time that is effective for maximizing yield of intended product.
  • NMR nuclear magnetic resonance
  • each reaction time independently may be from 30 minutes to 48 hours.
  • the Metallocene Precatalyst e.g., the Metallocene Precatalyst of Formula (B)
  • the metallocene precatalyst may be synthesized according to methods known in the art, including those methods referenced herein.
  • the metallocene precatalyst may be obtained from a precatalyst supplier such as Boulder Scientific.
  • the productivity enhanced bimodal catalyst is a product of an activation reaction of an activator, the activity-enhancing compound, and the aforementioned metallocene precatalyst and non-metallocene precatalyst, both as provided herein.
  • the Non-Metallocene Precatalyst (e.g., the Non-Metallocene Precatalyst of Formula (C)).
  • the non-metallocene precatalyst may be synthesized according to methods known in the art, including those methods referenced herein.
  • the non-metallocene precatalyst may be obtained from a precatalyst supplier such as Boulder Scientific.
  • the productivity enhanced bimodal catalyst is a product of an activation reaction of an activator, the activity- enhancing compound, and the aforementioned metallocene precatalyst and non-metallocene precatalyst, both as provided herein. Polyolefin polymer made by the method of polymerizing.
  • the polyolefin polymer made therefrom is an ethylene/propylene copolymer.
  • the polyolefin polymer made therefrom is a polyethylene homopolymer.
  • the polyolefin polymer made therefrom is a poly(ethylene-co-1-butene) copolymer, a poly(ethylene-co-1-hexene) copolymer, or a poly(ethylene-co-1-octene) copolymer.
  • the polyolefin polymer made from the 1-alkene monomer is an ethylene-based polymer having from 50 to 100 weight percent (wt%) repeat units derived from ethylene and from 50 to 0 wt% repeat units derived from a 1-alkene monomer selected from propylene, 1-butene, 1-hexene, 1-octene, and the combination of any two or more thereof.
  • the polymerization method uses the 1-alkene monomer and a comonomer that is a diene monomer (e.g., 1,3-butadiene).
  • the polyolefin polymer is an ethylene/propylene/diene monomer (EPDM) copolymer.
  • EPDM ethylene/propylene/diene monomer
  • the EPDM copolymer may be an ethylene/propylene/1,3-butadiene copolymer.
  • the Multimodal (e.g., trimodal) Catalyst System comprises the productivity enhanced bimodal catalyst and at least one different olefin polymerization catalyst selected from a metallocene catalyst and a different non-metallocene catalyst.
  • the multimodal catalyst system makes in a single reactor a multimodal polyethylene composition comprising an HMW polyethylene component, a medium MW component, and an LMW polyethylene component.
  • the method of making the productivity enhanced bimodal catalyst may be performed in the presence of the different olefin catalyst (e.g., a metallocene catalyst or a metallocene precatalyst).
  • the method of activating the non-metallocene precatalyst with an activator further comprises activating the different (e.g., metallocene) precatalyst with a same or different activator.
  • the method of making the productivity enhanced bimodal catalyst is performed in the absence of a different precatalyst. Unsupported or supported catalyst.
  • the non-metallocene precatalyst, the non- metallocene catalyst (made from the non-metallocene precatalyst), the metallocene precatalyst, the metallocene catalyst (made from the metallocene precatalyst), the productivity enhanced bimodal catalyst, and the multimodal catalyst system independently may be unsupported or disposed on a solid particulate support material.
  • the non-metallocene precatalyst, the non-metallocene catalyst, the metallocene precatalyst, the metallocene catalyst, the productivity enhanced bimodal catalyst, and the multimodal catalyst system may be injected into a slurry-phase, solution-phase, or gas-phase polymerization reactor as a solution in a hydrocarbon solvent.
  • the non-metallocene precatalyst, the non-metallocene catalyst, the metallocene precatalyst, the metallocene catalyst, the productivity enhanced bimodal catalyst, and the multimodal catalyst system is/are disposed on the support material, they may be injected into the slurry-phase, solution-phase, or gas-phase polymerization reactor as a slurry suspended in the hydrocarbon solvent or as a dry, powder (i.e., dry particulate solid).
  • the non-metallocene precatalyst, the non-metallocene catalyst (made from the non- metallocene precatalyst), the metallocene precatalyst, the metallocene catalyst (made from the metallocene precatalyst), the productivity enhanced bimodal catalyst, and/or the multimodal catalyst system may be premade in the absence of the support material and later disposed onto the support material.
  • the non-metallocene precatalyst, the non-metallocene catalyst, the metallocene precatalyst or the metallocene catalyst may be disposed onto the support material, and then the remaining of the non-metallocene catalyst and/or the metallocene catalyst of the productivity enhanced bimodal catalyst may be made in situ on the support material.
  • the non-metallocene precatalyst, the non-metallocene catalyst, the metallocene precatalyst, the metallocene catalyst, the productivity enhanced bimodal catalyst, and/or the multimodal catalyst system may be made by a concentrating method by evaporating a hydrocarbon solvent from a suspension or solution of the support material in a solution of the non-metallocene precatalyst, the non-metallocene catalyst, the metallocene precatalyst, the metallocene catalyst, the productivity enhanced bimodal catalyst, and/or the multimodal catalyst system in the hydrocarbon solvent.
  • the non-metallocene precatalyst, the non-metallocene catalyst, the metallocene precatalyst, the metallocene catalyst, the productivity enhanced bimodal catalyst, and/or the multimodal catalyst system may be made by a spray-drying method by spray-drying the suspension or solution. In some embodiments the spray-drying method is used.
  • the method can comprise combining the non-metallocene precatalyst, the metallocene precatalyst, the effective amount of the activator, the effective amount of the activity-enhancing compound, the support material, and an inert hydrocarbon solvent to make a mixture, and removing the inert hydrocarbon solvent from the mixture so as to give the productivity enhanced bimodal catalyst disposed on the support material.
  • the support material is a particulate solid that may be nonporous, semi-porous, or porous.
  • a carrier material is a porous support material. Examples of support materials are talc, inorganic oxides, inorganic chloride, zeolites, clays, resins, and mixtures of any two or more thereof.
  • suitable resins are polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins.
  • the support material independently may be an untreated silica, alternatively a calcined untreated silica, alternatively a hydrophobing agent-treated silica, alternatively a calcined and hydrophobing agent-treated silica.
  • the hydrophobing agent may be dichlorodimethylsilane.
  • Inorganic oxide support materials include Group 2, 3, 4, 5, 13 or 14 metal oxides.
  • the preferred supports include silica, which may or may not be dehydrated, fumed silica, alumina (see, for example, PCT Publication WO 99/60033), silica-alumina and mixtures thereof.
  • Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Pat. No.5,965,477), montmorillonite (EP 0511665), phyllosilicate, zeolites, talc, clays (U.S. Pat. No.6,034,187), and the like.
  • combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania and the like.
  • Additional support materials may include those porous acrylic polymers described in EP 0767184, which is incorporated herein by reference.
  • Other support materials include nanocomposites as disclosed in PCT Publication WO 99/47598; aerogels as disclosed in PCT Publication WO 99/48605; spherulites as disclosed in U.S. Pat. No.5,972,510; and polymeric beads as disclosed in PCT Publication WO 99/50311.
  • the support material may have a surface area in the range of from about 10 m 2 /g to about 700 m 2 /g, a pore volume in the range of from about 0.1 cm 3 /g to about 4.0 cm 3 /g, and average particle size in the range of from about 5 microns to about 500 microns.
  • the support material may be a silica (e.g., fumed silica), alumina, a clay, or talc.
  • the fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated).
  • the support is a hydrophobic fumed silica, which may be prepared by treating an untreated fumed silica with a hydrophobing agent such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane.
  • the treating agent is dimethyldichlorosilane.
  • the support is Cabosil® TS-610.
  • One or more precatalysts and/or one or more activators may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support or carrier materials.
  • the non-metallocene precatalyst and/or the metallocene precatalyst may be spray dried according to the general methods described in US5648310.
  • the support used with the productivity enhanced bimodal catalyst may be functionalized, as generally described in EP 0802203, or at least one substituent or leaving group is selected as described in US5688880.
  • Solution phase polymerization and/or slurry phase polymerization of olefin monomer(s) are well-known. See for example US8291115B2.
  • Inert hydrocarbon solvent An alkane, an arene, or an alkylarene (i.e., arylalkane).
  • alkanes such as mineral oil, pentanes, hexanes, heptanes, octanes, nonanes, decanes, undecanes, dodecanes, etc., and toluene, and xylenes.
  • the inert hydrocarbon solvent is an alkane, or a mixture of alkanes, where each alkane independently has from 5 to 20 carbon atoms, alternatively from 5 to 12 carbon atoms, alternatively from 5 to 10 carbon atoms.
  • Each alkane independently may be acyclic or cyclic. Each acyclic alkane independently may be straight chain or branched chain.
  • the acyclic alkane may be pentane, 1-methylbutane (isopentane), hexane, 1-methylpentane (isohexane), heptane, 1- methylhexane (isoheptane), octane, nonane, decane, or a mixture of any two or more thereof.
  • the cyclic alkane may be cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methycyclopentane, methylcyclohexane, dimethylcyclopentane, or a mixture of any two or more thereof.
  • suitable alkanes include Isopar-C, Isopar-E, and mineral oil such as white mineral oil.
  • the inert hydrocarbon solvent is free of mineral oil.
  • the inert hydrocarbon solvent may consist of one or more (C 5 -C 12 )alkanes.
  • GPP Gas-phase polymerization
  • the polymerization uses a GPP reactor, such as a stirred-bed gas phase polymerization reactor (SB-GPP reactor) or a fluidized-bed gas-phase polymerization reactor (FB-GPP reactor).
  • a GPP reactor such as a stirred-bed gas phase polymerization reactor (SB-GPP reactor) or a fluidized-bed gas-phase polymerization reactor (FB-GPP reactor).
  • SB-GPP reactor stirred-bed gas phase polymerization reactor
  • FB-GPP reactor fluidized-bed gas-phase polymerization reactor
  • the FB-GPP reactor/method may be as described in any one of US 3,709,853; US 4,003,712; US 4,011,382; US 4,302,566; US 4,543,399; US 4,882,400; US 5,352,749; US 5,541,270; US 2018/0079836 A1; EP-A-0802202; and Belgian Patent No.839,380.
  • SB- GPP and FB-GPP polymerization reactors and processes either mechanically agitate or fluidize by continuous flow of gaseous monomer and diluent the polymerization medium inside the reactor, respectively.
  • Other useful reactors/processes contemplated include series or multistage polymerization processes such as described in US 5,627,242; US 5,665,818; US 5,677,375; EP-A- 0794200; EP-B1-0649992; EP-A-0802202; and EP-B-634421
  • Gas phase polymerization operating conditions are any variable or combination of variables that may affect a polymerization reaction in the GPP reactor or a composition or property of a polyolefin polymer composition product made thereby.
  • the variables may include reactor design and size; precatalyst composition and amount; reactant composition and amount; molar ratio of two different reactants; presence or absence of feed gases such as H 2 , molar ratio of feed gases versus reactants, absence or concentration of interfering materials (e.g., H 2 O and/or O 2 ), absence or presence of an induced condensing agent (ICA), average polymer residence time in the reactor, partial pressures of constituents, feed rates of monomers, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, time periods for transitioning between steps. Variables other than that/those being described or changed by the method or use may be kept constant.
  • feed gases such as H 2 , molar ratio of feed gases versus reactants, absence or concentration of interfering materials (e.g., H 2 O and/or O 2 ), absence or presence of an induced condensing agent (ICA), average polymer residence time in the reactor, partial pressures of constituents, feed rates of monomers
  • control individual flow rates of ethylene (“C 2 ”), hydrogen (“H 2 ”) and 1- hexene (“C 6 ” or “C x ” where x is 6) or 1-butene (“4” or “C x ” where x is 4) to maintain a fixed comonomer to ethylene monomer gas molar ratio or feed mass ratio (C x /C 2 , e.g., C 6 /C 2 ) equal to a described value (e.g., 0.004 or 0.0016), a constant hydrogen to ethylene gas molar ratio or feed mass ratio (“H 2 /C 2 ”) equal to a described value (e.g., 0.002 or 0.004), and a constant ethylene (“C 2 ”) partial pressure equal to a described value (e.g., 1,034 kPa or 1586 kPa).
  • Maintain the fluidized bed at a constant height by withdrawing a portion of the bed at a rate equal to the rate of production of particulate form of the polyolefin polymer composition, which production rate may be from 5,000 to 150,000 kilograms per hour (kg/hour).
  • Remove the product polyolefin polymer composition semi-continuously via a series of valves into a fixed volume chamber, where this removed multimodal (e.g., bimodal or trimodal) ethylene-co-1- hexene copolymer composition is purged to remove entrained hydrocarbons and treated with a stream of humidified nitrogen (N 2 ) gas to deactivate any trace quantities of residual catalyst.
  • N 2 humidified nitrogen
  • the bimodal catalyst system may be fed into the polymerization reactor(s) in “dry mode” or “wet mode”, alternatively dry mode, alternatively wet mode.
  • the dry mode is a dry powder or granules.
  • the wet mode is a suspension in an inert liquid such as mineral oil.
  • Induced condensing agent (ICA) An inert liquid useful for cooling materials in GPP reactor(s). Its use is optional.
  • the ICA may be a (C 3 -C 20 )alkane, alternatively a (C 5 -C 20 )alkane, e.g., 2-methylbutane (i.e., isopentane).
  • ICA concentration in reactor may be from 0.1 to 25 mol%, alternatively from 1 to 16 mol%, alternatively from 1 to 10 mol%.
  • the GPP conditions may further include one or more additives such as a chain transfer agent or a promoter.
  • the chain transfer agents are well known and may be alkyl metal such as diethyl zinc. Promoters are known such as in US 4,988,783 and may include chloroform, CFCl 3 , trichloroethane, and difluorotetrachloroethane.
  • a scavenging agent Prior to reactor start up, a scavenging agent may be used to react with moisture and during reactor transitions a scavenging agent may be used to react with excess activator. Scavenging agents may be a trialkylaluminum. GPP may be operated free of (not deliberately added) scavenging agents. The GPP reactor/method may further include an amount (e.g., 0.5 to 200 ppm based on all feeds into reactor) of one or more static control agents and/or one or more continuity additives such as aluminum stearate or polyethyleneimine. The static control agent(s) may be added to the FB-GPP reactor to inhibit formation or buildup of static charge therein.
  • the GPP reactor may be a commercial scale FB-GPP reactor such as a UNIPOLTM reactor or UNIPOLTM II reactor, which are available from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company, Midland, Michigan, USA.
  • the 1-alkene monomer is ethylene, propylene, 1-butene, 1-hexene, 1-octene, or a combination of any two or more thereof. In some embodiments the 1-alkene monomer is a combination of ethylene and propylene. In other embodiments the 1-alkene monomer is ethylene alone or a combination of ethylene and 1-butene, 1-hexene, or 1-octene. Polyolefin polymer.
  • a product of polymerizing at least one 1-alkene monomer with the productivity enhanced bimodal catalyst A macromolecule, or collection of macromolecules, having constitutional units derived from the at least one 1-alkene monomer.
  • the polyolefin polymer consists of a polyethylene homopolymer.
  • the polyolefin polymer consists of an ethylene/propylene copolymer.
  • the polyolefin polymer is selected from a poly(ethylene-co-1-butene) copolymer, a poly(ethylene-co- 1-hexene) copolymer, and a poly(ethylene-co-1-octene) copolymer, respectively.
  • the polyolefin polymer may be a homopolymer or a copolymer.
  • the polyolefin polymer made from the productivity enhanced bimodal catalyst has a multimodal (e.g., bimodal) molecular weight distribution and comprises a higher molecular weight (HMW) polyolefin polymer component and a lower molecular weight (LMW) polyolefin polymer component.
  • HMW molecular weight
  • LMW lower molecular weight
  • the HMW polyolefin polymer component and the LMW polyolefin polymer component may be made by the productivity enhanced bimodal catalyst.
  • any compound, composition, formulation, material, mixture, or reaction product herein may be free of any one of the chemical elements selected from the group consisting of: H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, lanthanoids, and actinoids; with the proviso that chemical elements required by the compound, composition, formulation, material, mixture, or reaction product (e.g., Zr required by a zirconium compound, or C and H required by a polyethylene, or C, H, and O required by an
  • ASTM is the standards organization, ASTM International, West Conshohocken, Pennsylvania, USA. Any comparative example is used for illustration purposes only and shall not be prior art. Free of or lacks means a complete absence of; alternatively not detectable.
  • IUPAC International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, North Carolina, USA). Periodic Table of the Elements is the IUPAC version of May 1, 2018. May confers a permitted choice, not necessarily an imperative. Operative means functionally capable or effective. Optional(ly) means is absent (or excluded), alternatively is present (or included). Properties may be measured using standard test methods and conditions.
  • Ranges include endpoints, subranges, and whole and/or fractional values subsumed therein, except a range of integers does not include fractional values.
  • Room temperature 23 ° ⁇ 1 °C.
  • definitions of terms used herein are taken from the IUPAC Compendium of Chemical Technology (“Gold Book”) version 2.3.3 dated February 24, 2014. Some definitions are given below for convenience.
  • a “hydrocarbyl” or “hydrocarbyl group” includes aliphatic, cyclic, olefinic, acetylenic and aromatic radicals (i.e., hydrocarbon radicals) comprising hydrogen and carbon that are deficient by one hydrogen.
  • an “alkyl” includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen.
  • a —CH3 group (“methyl”) and a CH3CH2— group (“ethyl”) are examples of alkyls.
  • a “haloalkyl” includes any alkyl radical having one or more hydrogen atoms replaced by a halogen atom.
  • aryl groups include phenyl, naphthyl, pyridyl and other radicals whose molecules have the ring structure characteristic of benzene, naphthylene, phenanthrene, anthracene, etc.
  • an “aryl’ group can be a C6 to C20 aryl group.
  • a C6H5 ⁇ aromatic structure is an “phenyl”
  • a C6H42 ⁇ aromatic structure is an “phenylene.”
  • an “alkylene” includes linear, branched and cyclic hydrocarbon radicals deficient by two hydrogens.
  • —CH 2 — (“methylene”) and —CH 2 CH 2 — (“ethylene”) are examples of alkylene groups.
  • Reactor Additive The systems or polymerization processes using the productivity enhanced bimodal catalyst may optionally have at least one reactor additive.
  • the at least one reactor additive may be a flowability aid for preventing agglomeration of dry catalyst particles; an anti-static compound for inhibiting build-up of electrical charges on polyolefin particles in floating- bed gas phase polymerization reactors; or an anti-fouling compound such as a metal carboxylate salt for inhibiting reactor fouling.
  • Bimodal means a molecular weight distribution having two, and only two peaks as determined by GPC, where the two peaks can be a head and shoulder configuration or a two heads configuration having a local minimum (valley) therebetween. It can also refer to a catalyst that produces such a bimodal molecular weight distribution.
  • Catalyst herein means a material that can polymerize a monomer and optionally a comonomer so as to make a polymer.
  • the catalyst may be an olefin polymerization catalyst, which can polymerize an olefin monomer (e.g., ethylene) and optionally an olefin comonomer (e.g., propylene and/or a (C 4 -C 20 )alpha-olefin) so as to make a polyolefin homopolymer or, optionally, a polyolefin copolymer, respectively.
  • an olefin polymerization catalyst which can polymerize an olefin monomer (e.g., ethylene) and optionally an olefin comonomer (e.g., propylene and/or a (C 4 -C 20 )alpha-olefin) so as to make a polyolefin homopolymer or, optional
  • Catalyst system a set of at least two chemical constituents and/or reaction products thereof that together function as an integrated whole for enhancing rate of reaction, where at least one of the at least two chemical constituents is a catalyst.
  • the other chemical constituent(s) may be independently selected from a different catalyst, a support material, excess amount of activator, a catalyst additive such as an anti-static agent, a co-catalyst, a carboxylate metal salt, a dispersant for preventing particles of the catalyst system from sticking together.
  • the catalyst system may comprise a catalyst and a support material, where the catalyst is disposed on the support material, which hosts and provides a physical framework for increasing surface distribution of the catalyst.
  • Catalyst system does not include a monomer, a comonomer, or the activity-enhancing compound.
  • Activation The productivity enhanced bimodal catalyst is made by way of an activation. The activation takes place between the non-metallocene precatalyst, the metallocene precatalyst, the effective amount of the activator, and the effective amount of the activity-enhancing compound, which activates the non-metallocene precatalyst and the metallocene precatalyst into the productivity enhanced bimodal catalyst.
  • the productivity enhanced bimodal catalyst is made by converting the non-metallocene precatalyst and the metallocene precatalyst into the productivity enhanced bimodal catalyst having an enhanced polymer producing functionality (e.g., having at least improved (greater) productivity).
  • the activity-enhancing compound is free of a metal atom. Therefore, it is quite surprising that the activity-enhancing compound is capable of increasing the productivity of a catalyst made from the non-metallocene precatalyst and the metallocene precatalyst. Consisting essentially of means free of an exogenous organometallic compound.
  • the exogenous organometallic compound is compositionally different than the non-metallocene precatalyst and the metallocene precatalyst.
  • the inventive method is not achieved by adding an exogenous organometallic compound or precatalyst precursor thereof.
  • the contacting step of the method is performed in the absence of the exogenous organometallic compound or precatalyst precursor thereof.
  • the precatalysts are not self-modifying such that they cannot increase productivity of itself or another compound. Stated differently, in the absence of the activity-enhancing compound, there is no productivity increase.
  • Exogenous Having an external cause or origin or obtaining from an external source. Feeding.
  • GPC means gel permeation chromatography.
  • Leaving group A group bonded to the metal atom of a non-metallocene precatalyst and abstracted by an activator during the activation of the precatalyst to the non-metallocene catalyst. Examples of leaving groups are the monodentate group X in structural Formula (C). Each non- metallocene precatalyst described herein implicitly has at least one leaving group, and typically two leaving groups.
  • a monovalent, divalent, trivalent, or tetravalent and dicoordinate, tricoordinate or tetracoordinate organic group having two, three, or four, respectively coordinating functional groups for bonding to the metal atom of a non-metallocene precatalyst or a metallocene precatalyst.
  • the ligand remains coordinated to the metal atom in either the non-metallocene catalyst or the metallocene catalyst by activating the respective precatalyst.
  • “Productivity-increasing” or increase productivity means transforming a productivity of an olefin polymerization catalyst by increasing the productivity thereof as compared to a productivity of the olefin polymerization catalyst under the same polymerization conditions prior to chemically converting the olefin polymerization catalyst.
  • Multimodal means a molecular weight distribution having two or more peaks as determined by GPC, where the two or more peaks independently can be a head and shoulder configuration or a two or more heads configuration having a local minimum (valley) therebetween. Examples of multimodal are bimodal and trimodal. It can also refer to a catalyst that produces such a multimodal molecular weight distribution.
  • Organic compound means a chemical entity consisting of, per molecule, carbon atoms, hydrogen atoms, optionally zero, one or more halogen atoms, and optionally zero, one, or more heteroatoms independently selected from O, N, P, and Si.
  • the molecule does not have, i.e., is free of, a metal atom (i.e., the chemical entity does not include organometallic compounds).
  • Reaction conditions including polymerization conditions, are environmental circumstances such as temperature, pressure, solvent, reactant concentrations, and the like under which a chemical transformation (e.g., polymerization) proceeds. All chemical transformations described herein are conducted under suitable and effective reaction conditions.
  • Support material means a finely-divided, particulate inorganic solid capable of hosting a catalyst.
  • Trimodal means a molecular weight distribution having three, and only three peaks as determined by GPC. It can also refer to a catalyst that produces such a trimodal molecular weight distribution. Unsupported means free of an inorganic support material (e.g., silica).
  • Particle size was measured using a Malvern Mastersizer laser diffraction particle size analyzer (Malvern Panalytical). Differential Scanning Calorimetry Melt temperature was determined via Differential Scanning Calorimetry (DSC) according to ASTM D 3418-08. In general, a scan rate of 10 °C/min on a sample of 10 mg was used, and the second heating cycle was used to determine Tm.
  • GPC Gel-Permeation Chromatography
  • M w , M n , M z , M p and M w /M n (PDI) were determined using a High Temperature GPC (Polymer Laboratories), equipped with a differential refractive index detector (DRI).
  • the polymer solutions were prepared by placing dry polymer in glass vials, adding the desired amount of TCB, then heating the mixture at 160 °C with continuous shaking for about 2 hours. All quantities were measured gravimetrically. The injection concentration was from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. Prior to running each sample the DRI detector was purged. The flow rate in the apparatus was then increased to 1.0 ml/minute, and the DRI was allowed to stabilize for 8 hours before injecting the first sample. The molecular weight was determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards.
  • PS monodispersed polystyrene
  • the mass recovery was calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. All molecular weights are reported in g/mol unless otherwise noted.
  • the comonomer content (i.e., 1-hexene) incorporated in the polymers (weight % C6)) was determined by rapid FT-IR spectroscopy on the dissolved polymer in a GPC measurement.
  • Comonomer content can be determined with respect to polymer molecular weight by use of an infrared detector such as an IR5 detector in a gel permeation chromatography measurement, as described in Analytical Chemistry 2014, 86(17), 8649-8656. “Toward Absolute Chemical Composition Distribution Measurement of Polyolefins by High-Temperature Liquid Chromatography Hyphenated with Infrared Absorbance and Light Scattering Detectors” by Dean Lee, Colin Li Pi Shan, David M. Meunier, John W.
  • CC-A Comparative Catalyst A
  • CC-A Comparative Catalyst A
  • CC-A was prepared and sprayed in a nitrogen-purged glove box.
  • 1.37 g of fumed silica CAB-O-SIL® TS-610 Fumed Silica
  • Catalyst Compound (IV (0.013 g) was added, after which the mixture was allowed to stir for a further 30-60 minutes.
  • the mixture was spray-dried using a Buchi Mini Spray Dryer B-290 with the following parameters to yield the dried sample: Set Temperature of 140 °C, an outlet temperature of 75 °C (min.), aspirator setting of 70, and a pump speed of 130 rpm.
  • IC-1 was prepared and sprayed in a nitrogen-purged glove box.
  • IC-2 was prepared and sprayed in a nitrogen-purged glove box.
  • 1.37 g of fumed silica (CAB-O-SIL® TS-610 Fumed Silica) was slurried in 34 g of toluene until well dispersed, then 9.2 g of a 10 % solution by weight of MAO in toluene and Catalyst Compound (I) (0.045 g) were added.
  • CC-B Comparative Catalyst B
  • CC-B Comparative Catalyst B
  • CC-B Comparative Catalyst B
  • the mixture was spray-dried using a Buchi Mini Spray Dryer B-290 with the following parameters to yield the dried sample: Set Temperature of 140 °C, an outlet temperature of 75 °C (min.), aspirator setting of 70, and a pump speed of 130 rpm.
  • Gas-phase batch reactor catalyst testing procedure The spray dried catalysts prepared above were used for ethylene/1-hexene copolymerizations conducted in the gas-phase in a 2L semi-batch autoclave polymerization reactor. The individual run conditions and the properties of the polymers produced in these runs are seen in Tables 2A/2B.
  • the gas phase reactor employed was a 2-liter, stainless steel autoclave equipped with a mechanical agitator.
  • SMAO silicon supported methylaluminoxane
  • H2/C2 0.004
  • the reactor was cooled down, vented and opened.
  • the resulting product mixture was washed with water and methanol, then dried.
  • Polymerization Activity (grams polymer/gram catalyst-hour) was determined as the ratio of polymer produced to the amount of catalyst added to the reactor.
  • the maximum C2 uptake reached during the reactor for the inventive bimodal catalysts made with the activity enhancing compound (AEC) is lower, i.e., ⁇ 10.0 slpm (examples IE 1 and IE 2) while the bimodal catalyst without the AEC had much higher maximum ethylene uptake, i.e., > 12.0 slpm (example CE A).
  • a higher maximum ethylene uptake is also representative of a greater light-off, which corresponds to maximum internal reactor temperatures as reported in Table 2B.
  • the AEC can be given by the general formula (V) and the specific formulae (VI) to (VIII):
  • VII) Additive effectiveness index at 0.3 hours
  • AIE(0.3) ⁇ ⁇ 2(A.D) ⁇ ! ⁇ " #$ ⁇ 2(A.D)
  • the additive effectiveness indices (AEI(t)) are given in Tables 3A-3C.
  • Each AEI(t) for IE 1 and IE 2 were compared to the AEI(t) of CE A.
  • the AIE(t) values close to 1 indicated no significant change in the kinetics as shown by the ethylene uptake curves.
  • An AIE(t) > 1.5 indicate a significant impact on the kinetics of the catalyst.
  • the AEI(0.1), AEI(0.3), and AEI(0.9) are all greater, i.e., larger, than 1.8 for the inventive examples IE 1 and IE 2. Similar is observed for IE 3 and IE 4 compared to CE D.
  • the additive effectiveness index can also be used to show that there is no direct impact of the AEC on the metallocene compound (Table 3B).
  • the AEI(0.1), AIEI(0.3), and AEI(0.1) values are all close to 1, indicating no significant change to the kinetics of the metallocene with the addition of the AEC. Additionally, the lower productivity (17,949 compared to 19,710) coupled with the slightly lower maximum C2 uptake (12.980 slpm compared to 13.068 slpm) of CE B compared to that of CE C indicate a poisoning effect of the additive compound on the metallocene when contacted directly and not as part of the bimodal catalyst system. The lifetime of the catalyst can be quantified from the same semi-batch reactor test as described above.
  • the productivity enhanced bimodal catalyst IC 1 (example IE 1) has a longer lifetime than the comparative catalyst CC A (example CE A), which is quantified by having a lower maximum instantaneous ethylene uptake (i.e., 9.959 slpm vs 12.068 splm), but having greater, i.e., larger, instantaneous uptake values at time points if the reaction.
  • the lifetime can also be expressed as the ratio of the uptake at a given time (t) and is denoted by the Greek letter zeta, i.e., ⁇ (t).
  • the Activity-enhancing compound (II- a) modified the HMW catalyst component, Catalyst Compound (I), and was mixed with Catalyst Compound (I) and in the presence of the activator (e.g., MAO).
  • the Activity-enhancing compound (II-a) had no direct positive impact on the metallocene component (compounds (III) and (IV)).
  • Tint 114.3 °C compared to 108.3 and 107.5 °C for IE-1 and IE-2.
  • This feature is significant as a rapid light-off can be detrimental to reactor operability and result in chunks such as “catballs” where the heat associated with the rapid light-off can cause rapid agglomeration where large chunks of polymer grow around the injection tube.
  • the difference in temperature from the light-off can be seen in FIGS.1-3.
  • FIG.1 shows the max Tint for CE-A, IE-1 and IE-2. Not only is the max. Tint lower for IC-1 and IC-2, it takes longer for the max Tint to be reached. Both features are beneficial to running catalysts.
  • the Activity-enhancing compound (II-a) changes the kinetics of the HMW catalyst (believed to chemically modifiers the leaving group), which has a positive impact on the bimodal catalyst comprised of both HMW, Catalyst Compound (I), and LMW, Catalyst Compound (IV), components.
  • the higher IC-1 uptakes after 0.1 hours (which continues to 1 hr, and longer) means more catalyst over a longer time period, which is particularly significant for continuous gas phase polymerization reactors where average residence times can be 3 hours and longer. Similar trends shown in FIG.6 by the same catalysts, but under condition B.
  • FIG.5 shows the two comparative metallocene catalysts and the Activity-enhancing compound (II-a) are not directly impacted on the IC-1 uptake (kinetics and lifetime) of the metallocene catalyst.
  • FIG.7 provides polymer GPC traces from CE-A and IE-1, the only difference in catalyst composition being the AEC in IE-1. IE-1 had a 60% increase in productivity and the GPC show increased low molecular polymer component demonstrating the indirect effect of the AEC on the metallocene component.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un procédé de fabrication d'un catalyseur bimodal à productivité améliorée, le procédé comprenant la combinaison d'un précatalyseur non métallocène, d'un précatalyseur métallocène, d'une quantité efficace d'un activateur et d'une quantité efficace d'un composé améliorant l'activité pour activer le précatalyseur non métallocène et le précatalyseur métallocène dans le catalyseur bimodal à productivité améliorée.
PCT/US2024/053204 2023-12-12 2024-10-28 Additif pour catalyseur Pending WO2025128219A1 (fr)

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