WO2026006272A1 - Procédés de polymérisation en phase gazeuse pour la fabrication de polymère à base d'éthylène à l'aide de systèmes catalytiques contenant des 2-amino-thiazoles - Google Patents

Procédés de polymérisation en phase gazeuse pour la fabrication de polymère à base d'éthylène à l'aide de systèmes catalytiques contenant des 2-amino-thiazoles

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Publication number
WO2026006272A1
WO2026006272A1 PCT/US2025/034990 US2025034990W WO2026006272A1 WO 2026006272 A1 WO2026006272 A1 WO 2026006272A1 US 2025034990 W US2025034990 W US 2025034990W WO 2026006272 A1 WO2026006272 A1 WO 2026006272A1
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WIPO (PCT)
Prior art keywords
aryl
hydrocarbyl
activator
procatalyst
polyethylene
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Pending
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PCT/US2025/034990
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English (en)
Inventor
Andrew M. Camelio
Mary E. Garner
Brad C. Bailey
Rhett A. BAILLIE
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication of WO2026006272A1 publication Critical patent/WO2026006272A1/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
    • 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
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor

Definitions

  • the polyethylene and polypropylene polymerization process can be varied in a number of respects to produce a wide variety of resultant polyethylene resins having different physical properties tha t render the various resins suitable for use in different applications.
  • Polyethylene is produced via various catalyst systems. Selection of such catalyst systems used in the polymerization process of the polyethylene is an important factor contributing to the characteristics and properties of the polyethylene. BRIEF SUMMARY [0003] Despite previous research efforts in developing catalyst systems suitable for polyethylene polymerization, there is still a need to increase the efficiencies of catalyst systems to reduce their cost-in-use, particularly without compromising other critical properties such as the weight average molecular weight of the polymer formed, before any blending with other polymers and comonomer incorporation.
  • polyethylene polymers may be utilized for a number of products including films, fibers, pipes, nonwoven and/or woven fabrics, extruded articles, and/or molded articles, among others. There is continued focus in the industry on developing new and improved materials and/or processes that may be utilized to form these polymers.
  • Embodiments of the present disclosure meet this need by providing methods of making polyethylene in a gas phase reactor, which utilize a catalyst system comprising a procatalyst as described further herein. 86021-WO-PCT/DOW 86021 WO [0004]
  • Some specific embodiments further meet this need by providing methods of making polyethylene, which utilize the procatalyst as part of supported catalyst systems or a spray - dried supported catalyst systems.
  • Embodiments of the present disclosure are directed to methods of making polyethylene comprising: polymerizing in a gas phase reactor ethylene monomer and optionally at least one C3 to C81-alkene comonomer and a catalyst system, thereby forming a polyethylene, the catalyst system comprising a procatalyst having a structure according to Formula (I): where: M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +3 or +4; each X is a monodentate or bidentate ligand independently chosen from unsaturated (C 2 ⁇ C 30 )hydrocarbon, unsaturated (C 2 ⁇ C 30 )heterohydrocarbon, (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, halogen, ⁇ N(R X )2, and
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term “polymer” thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomer types.
  • Polyethylene or “ethylene-based polymer” refers to polymers comprising greater than 50% by weight derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more monomer types).
  • LDPE Low-density polyethylene
  • LLDPE Linear Low-density polyethylene
  • ULDPE Ultra Low-density polyethylene
  • VLDPE Very Low-density polyethylene
  • m-LLDPE linear low-density resins
  • MDPE Medium Density Polyethylene
  • HDPE High Density Polyethylene
  • LLDPE includes resin made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as “m-LLDPE”), phosphinimine, and constrained geometry catalysts, and resins made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts).
  • LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in U.S.
  • the LLDPE resins can be made via gas-phase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.
  • the term “HDPE” generally refers to polyethylenes having densities greater than about 0.940 g/cm 3 and up to about 0.970 g/cm 3 , which are generally prepared with Ziegler- Natta catalysts, chrome catalysts or single-site catalysts including, but not limited to, substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocene), constrained geometry catalysts, phosphinimine catalysts & polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy).
  • R 1 , R 2 , R 3 , R 4 , and R 5 may all be substituted alkyls or R 1 and R 2 may be a substituted alkyl and R 3 may be an aryl, etc.).
  • Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent, includes hexanes).
  • a named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name.
  • a parenthetical expression having the form “(Cx ⁇ Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y.
  • a (C 1 ⁇ C 30 )alkyl is an alkyl group having from 1 to 30 carbon atoms in its unsubstituted form.
  • certain chemical groups may be substituted by one or more substituents such as R S .
  • substitution means that at least one hydrogen atom ( ⁇ H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ).
  • substitution means that every hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ).
  • polysubstitution means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by a substituent.
  • ⁇ H means a hydrogen or hydrogen radical that is covalently bonded to another atom.
  • (C 1 ⁇ C 30 )hydrocarbyl means a hydrocarbon radical of from 1 to 30 carbon atoms and the term “(C1 ⁇ C30)hydrocarbylene” means a hydrocarbon diradical of from 1 to 30 carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (having three carbons or more, and including mono- and poly-cyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and substituted by one or more R S or unsubstituted.
  • Examples of (C 1 ⁇ C 50 )hydrocarbyl are unsubstituted or substituted (C1 ⁇ C50)alkyl, (C3 ⁇ C50)cycloalkyl, (C3 ⁇ C20)cycloalkyl-(C1 ⁇ C20)alkylene, (C6 ⁇ C40)aryl, or (C6 ⁇ C20)aryl-(C1-C20)alkylene (such as benzyl ( ⁇ CH2 ⁇ C6H5)).
  • (C1 ⁇ C50)alkyl means a saturated straight or branched hydrocarbon radical of from 1 to 50 carbon atoms that is unsubstituted or substituted by one or more R S.
  • alkyl groups e.g., (C x ⁇ C y )alkyl
  • R S R S
  • Each (C 1 ⁇ C 5 )alkyl may be methyl, trifluoromethyl, ethyl, 1- propyl, 1-methylethyl, or 1,1-dimethylethyl.
  • (C6 ⁇ C40)aryl means an unsubstituted or substituted (by one or more R S ) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 40 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms.
  • substituted (C 6 ⁇ C40)aryl examples include: substituted (C1 ⁇ C20)aryl; substituted (C6 ⁇ C18)aryl; 2,4-bis([C20]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.
  • (C3 ⁇ C50)cycloalkyl means a saturated cyclic hydrocarbon radical of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more R S .
  • Examples of substituted (C3 ⁇ C40)cycloalkyl are substituted (C3 ⁇ C20)cycloalkyl, substituted (C3 ⁇ C10)cycloalkyl, cyclopentanon-2-yl, and 1- fluorocyclohexyl.
  • Examples of (C 1 ⁇ C 50 )hydrocarbylene include unsubstituted or substituted (C 6 ⁇ C 50 )arylene, (C 3 ⁇ C 50 )cycloalkylene, and (C 1 ⁇ C 50 )alkylene (e.g., (C 1 ⁇ C 20 )alkylene).
  • (C2 ⁇ C20)alkylene ⁇ , ⁇ - diradicals include ethan-1,2-diyl (i.e. ⁇ CH2CH2 ⁇ ), propan-1,3-diyl (i.e. ⁇ CH2CH2CH2 ⁇ ), 2- methylpropan-1,3-diyl (i.e. ⁇ CH2CH(CH3)CH2 ⁇ ).
  • (C6 ⁇ C50)arylene ⁇ , ⁇ - diradicals include phenyl-1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.
  • (C 1 ⁇ C 50 )alkylene means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 50 carbon atoms that is unsubstituted or substituted by one or more R S .
  • Other alkylenee groups e.g., (Cx ⁇ Cy)alkylene are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more R S .
  • substituted (C1 ⁇ C50)alkylene examples include substituted (C1 ⁇ C20)alkylene, ⁇ CF2 ⁇ , ⁇ C(O) ⁇ , and ⁇ (CH2)14C(CH3)2(CH2)5 ⁇ (i.e., a 6,6-dimethyl substituted normal-1,20-eicosylene).
  • examples of substituted (C1 ⁇ C50)alkylene also include l,2-bis(methylene)cyclopentane, 1,2- bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3- bis (methylene)bicyclo [2.2.2] octane.
  • (C 3 ⁇ C 50 )cycloalkylene means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more 86021-WO-PCT/DOW 86021 WO R S .
  • Other cycloalkylene groups e.g., (Cx ⁇ Cy)cycloalkylene
  • (Cx ⁇ Cy)cycloalkylene are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more R S .
  • heteroatom refers to an atom other than hydrogen or carbon.
  • heterohydrocarbon refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom.
  • (C1 ⁇ C50)heterohydrocarbyl means a heterohydrocarbon radical of from 1 to 50 carbon atoms
  • (C1 ⁇ C50)heterohydrocarbylene means a heterohydrocarbon diradical of from 1 to 50 carbon atoms.
  • the heterohydrocarbon of the (C 1 ⁇ C 50 )heterohydrocarbyl or the (C 1 ⁇ C 50 )heterohydrocarbylene has one or more heteroatoms.
  • the radical of the heterohydrocarbyl may be on a carbon atom or a heteroatom.
  • the two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom.
  • one of the two radicals of the diradical may be on a carbon atom and the other radical may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom.
  • Each (C 1 ⁇ C 50 )heterohydrocarbyl and (C 1 ⁇ C 50 )heterohydrocarbylene may be unsubstituted or substituted (by one or more R S ), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic), or acyclic.
  • heterohydrocarbyl groups e.g., (Cx ⁇ Cy) heterohydrocarbyl
  • (Cx ⁇ Cy) heterohydrocarbyl are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more R S .
  • the (C 1 ⁇ C 50 )heterohydrocarbyl may be unsubstituted or substituted.
  • Non-limiting examples of the (C 1 ⁇ C 50 )heterohydrocarbyl include (C 1 ⁇ C 50 )heteroalkyl, (C 1 ⁇ C 50 )hydrocarbyl-O ⁇ , (C 1 ⁇ C 50 )hydrocarbyl-S ⁇ , (C 1 ⁇ C 50 )hydrocarbyl-S(O) ⁇ , (C 1 ⁇ C 50 )hydrocarbyl-S(O) 2 ⁇ , (C 1 ⁇ C 50 )hydrocarbyl-Si(R C ) 2 ⁇ , (C l ⁇ C 50 )hydrocarbyl-N(R N ) ⁇ , (C l ⁇ C 50 )hydrocarbyl-P(R P ) ⁇ , (C 2 ⁇ C 50 )heterocycloalkyl, (C 2 ⁇ C 19 )heterocycloalkyl- (C 1 ⁇ C 20 )alkylene, (C 3 ⁇ C 20 )cyclo
  • the (C1 ⁇ C30)heterohydrocarbyl may be unsubstituted or substituted.
  • Non-limiting examples of the (C1 ⁇ C30)heterohydrocarbyl include (C1 ⁇ C30)heteroalkyl, (C1 ⁇ C30)hydrocarbyl-O ⁇ , (C1 ⁇ C30)hydrocarbyl-S ⁇ , (C1 ⁇ C30)hydrocarbyl-S(O) ⁇ , (C1 ⁇ C30)hydrocarbyl-S(O)2 ⁇ , (C1 ⁇ C30)hydrocarbyl-Si(R C )2 ⁇ , (Cl ⁇ C30)hydrocarbyl-N(R N ) ⁇ , (Cl ⁇ C30)hydrocarbyl-P(R P ) ⁇ , (C2 ⁇ C30)heterocycloalkyl, (C2 ⁇ C20)heterocycloalkyl- (C1 ⁇ C10)alkylene, (C3 ⁇ C20)cyclo
  • (C 3 ⁇ C 50 )heteroaryl means an unsubstituted or substituted (by one or more R S ) mono-, bi-, or tricyclic heteroaromatic hydrocarbon radical of from 3 to 50 total carbon atoms and from 1 to 10 heteroatoms.
  • a monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical h as two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic.
  • the other ring or rings of the heteroaromatic radical may be independently fused or non-fused and aromatic or non-aromatic.
  • Other heteroaryl groups e.g., (C x ⁇ C y )heteroaryl generally, such as (C 4 ⁇ C 12 )heteroaryl
  • (C x ⁇ C y )heteroaryl are defined in an analogous manner as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one R S .
  • the monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring.
  • the 5-membered ring has 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S, N, or P.
  • Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1- yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl.
  • the 6-membered ring has 6 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1 or 2 and the heteroatoms may be N or P.
  • 6-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl.
  • the bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. 86021-WO-PCT/DOW 86021 WO Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol- 1-yl; and benzimidazole-1-yl.
  • Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl.
  • the tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system.
  • An Example of the fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl.
  • An Example of the fused 5,6,6-ring system is 1H-benzo[f] indol-1-yl.
  • An Example of the fused 6,5,6-ring system is 9H-carbazol-9-yl.
  • (C 1 ⁇ C 50 )heteroalkyl means a saturated straight or branched chain radicals containing one to fifty carbon atoms, or fewer carbon atoms and one or more of the heteroatoms.
  • (C1 ⁇ C50)heteroalkylene means a saturated straight or branched chain diradicals containing from 1 to 50 carbon atoms and one or more than one heteroatoms.
  • the heteroatoms of the heteroalkyls or the heteroalkylenes may include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, SR C , S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or are substituted by one or more R S .
  • Examples of unsubstituted (C2 ⁇ C40)heterocycloalkyl include unsubstituted (C2 ⁇ C20)heterocycloalkyl, unsubstituted (C2 ⁇ C10)heterocycloalkyl, aziridin-l-yl, oxetan-2- yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholin-4- yl, 1,4- dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza- cyclodecyl.
  • halogen atom or “halogen” means the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I).
  • halide means the anionic form of the halogen atom: fluoride (F ⁇ ), chloride (Cl ⁇ ), bromide (Br ⁇ ), or iodide (I ⁇ ).
  • saturated means lacking carbon–carbon double bonds, carbon–carbon triple bonds, and (in heteroatom-containing groups) carbon–nitrogen, carbon–phosphorous, and carbon–silicon double bonds.
  • one or more double and/or triple bonds optionally may or may not be present in substituents R S .
  • the term “unsaturated” means containing one or more carbon– carbon double bonds, carbon–carbon triple bonds, or (in heteroatom-containing groups) one or more carbon–nitrogen, carbon–phosphorous, or carbon–silicon double bonds, not 86021-WO-PCT/DOW 86021 WO including double bonds that may be present in substituents R S , if any, or in (hetero) aromatic rings, if any.
  • a method of making polyethylene may comprise polymerizing, in a gas phase reactor, ethylene monomer and optionally at least one C3 to C8 1-alkene comonomer and a catalyst system, thereby forming a polyethylene.
  • the polymerization may occur in a gas-phase polymerization reactor, such as a gas ⁇ phase fluidized bed polymerization reactor. Exemplary gas -phase systems are described in U.S. Patent Nos.5,665,818; 5,677,375; and 6,472,484; and European Patent Nos. 0 517 868 and 0 794 200.
  • the catalyst system may be fed to the gas-phase polymerization reactor in neat form (i.e., as a dry solid), or as a slurry.
  • particles of the catalyst system may be fed directly to the gas-phase polymerization reactor.
  • a slurry of catalyst system in a solvent such as an inert hydrocarbon liquid or mineral oil, may be fed to the reactor.
  • the gas-phase polymerization reactor comprises a fluidized bed reactor.
  • a fluidized bed reactor may include a “reaction zone” and a “velocity reduction zone.”
  • the reaction zone may include a bed of growing polymer particles, formed polymer particles, and a minor amount of the catalyst system fluidized by the continuous flow of the gaseous monomer and diluent to remove heat of polymerization through the reaction zone.
  • some of the re-circulated gases may be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone. Additional reactor details and means for operating the reactor are described in, for example, U.S. Patent Nos.
  • the gas phase polymerization occurs in the reactor at a temperature of less than or equal to 130 °C.
  • the reactor temperature of the gas -phase polymerization reactor may be from 75 oC to 115 oC, from 30 °C to 45 °C, from 45 °C to 60 °C, from 60 °C to 70 °C, from 70 °C to 75 °C, from 75 °C to 80 °C, from 80 °C to 85 °C, 86021-WO-PCT/DOW 86021 WO from 85 °C to 90 °C, from 90 °C to 95 °C, from 95 °C to 100 °C, from 100 °C to 105 °C, from 105 °C to 110 °C, from 110 °C to 115 °C, from 115 °C to 130 °C,, or any combination of two or more of these ranges.
  • the reactor pressure of the gas-phase polymerization reactor is from 690 kPa (100 psig) to 3,448 kPa (500 psig).
  • the reactor pressure of the gas - phase polymerization reactor may be from 690 kPa (100 psig) to 1,379 kPa (200 psig), from 1,379 kPa (200 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2,759 kPa (400 psig), from 2,759 kPa (400 psig) to 3,448 kPa (500 psig), or any combination of two or more of these ranges.
  • ethylene may be one of the gasses used to pressurize the gas-phase polymerization reactor.
  • the ethylene partial pressure may be up to 2413 kPa (350 psig), such as from 35 kpa (5 psig) to 137 kPa (20 psig), from 137 kPa (20 psig) to 345 kPa (50 psig), from 345 kPa (50 psig) to 689 kPa (100 psig), from 689 kPa (100 psig) to 1034 kPa (150 psig), from 1034 kPa (150 psig) to 1378 kPa (200 psig), from 1378 kPa (200 psig) to 1723 kPa (250 psig), from 1723 kPa (250 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig), from 2068 kPa (300 psig) to 24
  • hydrogen gas may be used during polymerization to control the final properties of the polyethylene.
  • the amount of hydrogen used during polymerization may be expressed as a mole ratio relative to the total polymerizable monomer, such as, for example, ethylene or a blend of ethylene and C3 to C81-alkene.
  • the amount of hydrogen used in the polymerization process may be an amount necessary to achieve the desired properties of the polyethylene, such as, for example, melt flow rate.
  • the mole ratio of hydrogen to total polymerizable monomer e.g., H2:monomer, also referred to herein as “H2:C2” or “H2/C2” is greater than 0.0001.
  • the mole ratio of hydrogen to total polymerizable monomer may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0 to 0.1, from 0.0001 to 0.10, from 0.0001 to 0.001, from 0.0001 to 0.0005, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.001, from 0.001 to 1.8, from 0.001 to 1.0, from 0.001 to 0.10, from 0.001 to 0.05, or from 0.001 to 0.005, or any combination of two or more of these ranges.
  • total polymerizable monomer refers to the amount of ethylene in the reactor which has not yet been covalently bonded to 86021-WO-PCT/DOW 86021 WO another compound, or the total amount of ethylene and C3 to C8 alkene comonomer in the reactor which has not yet been covalently bonded to another compound.
  • the ratio between at least one C3 to C81-alkene comonomer to the ethylene monomer (also referred to herein as a comonomer-to-ethylene ratio, or C 6 /C 2 ) in the polymerization reactor may be from 0 to 0.04, such as from 0 to 0.0001, from 0.0001 to 0.001, from 0.001 to 0.04, from 0.001 to 0.02, from 0.001 to 0.01, from 0.01 to 0.02, from 0.02 to 0.03, from 0.03 to 0.04, or any combination of two or more of these ranges.
  • the polymerization process produces greater than or equal to 300 grams of the polyethylene per grams of the spray-dried catalyst system per hour (gpoly/gcat ⁇ hour). In some embodiments, the process produces at to 400 gpoly/gcat ⁇ hour, at least 450 g poly /g cat ⁇ hour, at least 500 g poly /g cat ⁇ hour, at least 600 g poly /g cat ⁇ hour, at least 700 gpoly/gcat ⁇ hour, at least 800 gpoly/gcat ⁇ hour, at least 900 gpoly/gcat ⁇ hour, at least 1000 gpoly/gcat ⁇ hour, at least 1200 gpoly/gcat ⁇ hour, at least 1500 gpoly/gcat ⁇ hour, at least 2000 g poly /g cat ⁇ hour, at least 5,000 g poly /g cat ⁇ hour, or at least 75,000 g poly /g cat ⁇ hour.
  • the polymerization process consumes both ethylene and C3 to C8 1-alkene comonomer resulting in a comonomer uptake as defined by (wt. of C 3 to C 8 1-alkene comonomer consumed / wt. of ethylene consumed) x 100%.
  • comonomer uptake is a direct indicator of how well a catalyst system incorporates the comonomer. It is believed that ultra-low incorporation of comonomer, as is achieved in some embodiments by catalyst systems described herein, allows for the production of particu lar resins.
  • the comonomer uptake is ⁇ 4.0%, ⁇ 3.5%, ⁇ 3.0%, ⁇ 2.5%, ⁇ 2.0%, ⁇ 1.5%, ⁇ 1.0%., ⁇ 0.5%, from 0.001 to 4 %, from 0.001 to 0.01 %, from 0.01 % to 0.1 %, from 0.1 % to 0.15 %, from 0.15% to 0.2%, from 0.2 % to 0.25%, from 0.25% to 0.3%, from 0.3% to 0.35%, from 0.35% to 0.4%, or any combination of two or more of these ranges.
  • the method of making polyethylene may comprise polymerizing, via gas phase polymerization, ethylene monomer and optionally at least one C 3 to C 8 1-alkene comonomer and a catalyst system.
  • the optional at least one C 3 to C 8 1- 86021-WO-PCT/DOW 86021 WO alkene comonomer may comprise any C3 to C81-alkene comonomer, such as a 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene.
  • the catalyst system may comprise at least a procatalyst.
  • the term “procatalyst” refers to a compound that has catalytic activity when combined with an activator.
  • activator refers to a compound that chemically reacts with a procatalyst in a manne r that converts the procatalyst to a catalytically active catalyst.
  • activating co-catalyst and “activator” are interchangeable terms.
  • M is a metal.
  • M is chosen from titanium, zirconium, or hafnium.
  • M is zirconium or hafnium.
  • Each X is a monodentate or bidentate ligand independently chosen from unsaturated (C2 ⁇ C30)hydrocarbon, unsaturated (C2 ⁇ C30)heterohydrocarbon, (C1 ⁇ C30)hydrocarbyl, (C 1 ⁇ C 30 )heterohydrocarbyl, (C 6 -C 30 )aryl, (C 3 -C 30 )heteroaryl, halogen, ⁇ N(R X ) 2 , and ⁇ (CH 2 ) w Si(R X ) 3 , where w is 1 to 10 and each R X is independently selected from a (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6-C30)aryl, and (C3-C30)heteroaryl.
  • n 1 or 2.
  • Q is a monoanionic spectator ligand selected from (C1 ⁇ C50)hydrocarbyl, (C 1 ⁇ C 50 )heterohydrocarbyl, (C 5 -C 30 )aryl, and (C 3 -C 30 )heteroaryl, wherein Q is different from each X;
  • R 1 is a (C 1 ⁇ C 50 )hydrocarbyl, (C 1 ⁇ C 50 )heterohydrocarbyl, (C 6 -C 30 )aryl, or (C 3 - C30)heteroaryl.
  • Each R 2 and R 3 is independently selected from the group consisting of (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, ⁇ OR C , ⁇ Si(R C ) 3 , ⁇ Ge(R C ) 3 , halogen, and –H, wherein R 2 and R 3 are optionally covalently linked to form an aromatic ring or a non-aromatic ring.
  • Each R C is independently selected from the 86021-WO-PCT/DOW 86021 WO group consisting of (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6-C30)aryl, (C3- C 30 )heteroaryl, and –H.
  • each X is independently selected from (C1 ⁇ C10)alkyl, (C6 ⁇ C20)aryl, or a halogen; and each R1 is a (C1 ⁇ C30)alkyl, or a (C6 ⁇ C30)aryl.
  • Formula (I) is overall charge neutral.
  • R1 is (C6 ⁇ C30)aryl.
  • R 1 is selected from the group consisting of 2- methylphenyl, 2-(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-di(iso- propyl)phenyl, 2,4,6 tri(iso-propyl)phenyl, 3,5-di(tert-butyl)phenyl, 3,5-diphenylphenyl, 2,3,5,6-tetra-fluorophenyl, and 2-(1-naphthyl)phenyl.
  • R 1 is (C 1 ⁇ C 12 )alkyl, (C 1 ⁇ C 12 )cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl.
  • the (C1 ⁇ C30)hydrocarbyl of R2 and R3 may be a (C 6 ⁇ C 30 )aryl and the (C 1 ⁇ C 30 )heterohydrocarbyl of R 2 and R 3 may be a (C 3 ⁇ C 30 )heteroaryl.
  • each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, or chloro.
  • R2 and R3 are covalently linked to form a ring.
  • the procatalyst has a structure according to Formula (II): [0056] In Formula (II), each R1, Q, X, n, and M are defined as in Formula (I); and each R 4 , R 5 , R 6 , and R 7 are independently (C1 ⁇ C40)hydrocarbyl, (C1 ⁇ C40)heterohydrocarbyl, (C6- C 40 )aryl, (C 3 -C 40 )heteroaryl, a halogen, or –H. [0057] In various embodiments, R4 is (C6 ⁇ C40)aryl or (C3 ⁇ C40)heteroaryl.
  • R4 is phenyl, (2,4,6-tri-iso-propyl)phenyl, 2,4,6- trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert-butyl)phenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl.
  • R5, R6, and R7 are –H.
  • R 1 is (C 6 ⁇ C 30 )aryl
  • R 4 is phenyl, 2,4,6-tri(iso- propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert-butyl)phenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl
  • R 5, R 6 , and R 7, are ⁇ H.
  • Q is a monoanionic spectator ligand selected from (C1 ⁇ C50)hydrocarbyl, (C1 ⁇ C50)heterohydrocarbyl, (C5–C30)aryl, and (C3–C30)heteroaryl, wherein Q is different from each X.
  • Q may be unsubstituted or substituted cyclopentadienyl.
  • heteroleptic nature of the 2-amino-thiazole complexes described herein i.e., wherein Q is different from each X, may be advantageous for achieving improved catalyst activity and tunable polymer properties, relative to homoleptic 2-amino-thiazole complexes wherein the ligands bonded to the metal center, other than the 2-amino-thiazole ligand, are the same (e.g., three benzyl ligands).
  • heteroleptic 2-amino-thiazole complexes described herein have increased catalyst activities relative to their homoleptic analogs, or produce polymers with low comonomer incorporation and variable weight-average molecular weight, the combination of which is believed to be favorable for polymer processability, or a combination of both.
  • Q is chosen from formulas (III), (IV), (V), or (VI); where the wavy line indicates a point of attachment to the M of Formula (I): Formula (III); 86021-WO-PCT/DOW 86021 WO R 8 , R 9 , and R 10 may be independently chosen from (C 1 ⁇ C 30 )hydrocarbyl, (C 1 - C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl.
  • R11 R12, R13, and R14 may be independently chosen from the group consisting of (C1 ⁇ C30)hydrocarbyl, (C 1 ⁇ C 30 )heterohydrocarbyl, (C 6 –C 30 )aryl, (C 3 –C 30 )heteroaryl, ⁇ Si(R C ) 3 , ⁇ Ge(R C ) 3 , ⁇ N(R N ) 2 , ⁇ OR C , and –H.
  • Each R N and R C may be independently selected from the group consisting of (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H.
  • R 11 and R 12 , or R 11 and R 13 , or R 11 and R 14 , or R 13 and R 14 , or R 12 and R 13 , or R 12 and R 14 may be covalently connected to form an aromatic ring or non-aromatic ring.
  • R 15 , R 16 , R17, R18, R19, R20, R21, R22, R23, R24, R25, and R26 may be independently chosen from –H, (C1- C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, ⁇ Si(R C )3, or -Ge(R C ) 3 .
  • R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 18 and R 19 , R 20 and R 21 , R 21 and R22, R22 and R23, R24 and R25, or R25 and R26 are covalently linked to form one or more ring or multi-ring structures.
  • R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, and R 26 are independently chosen from –H and (C 1 -C 10 )alkyl.
  • procatalysts are disclosed as formulas (IIa) through (IIm): 86021-WO-PCT/DOW 86021 WO Formula (IIc) Formula (IId) Formula (IIe) Formula (IIf) 86021-WO-PCT/DOW 86021 WO 86021-WO-PCT/DOW 86021 WO Supported Catalyst Systems
  • the catalyst system is a supported catalyst system comprising: the procatalyst; an activator; and a support.
  • the procatalyst may be rendered catalytically active by contacting it to, or combining it with, an activator.
  • the term “activator” may include any combination of reagents that increases the rate at which a procatalyst oligomerizes or polymerizes unsaturated monomers, such as olefins. An activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer produced.
  • the procatalyst may be activated for oligomerization and/or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and or polymerization.
  • the activator is a supported activator, that is, the activator is supported on a support material.
  • Alumoxane activators may be utilized as an activator for one or more of the procatalysts described herein.
  • Alumoxane(s) or aluminoxane(s) are generally oligomeric compounds containing –Al(R)–O– subunits, where R is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide.
  • the activator comprises methylalumoxane (MAO).
  • MAO methylalumoxane
  • the molar ratio of metal in the activator to metal in the procatalyst is from 0.5:1 to 3500:1, such as from 0.5:1 to 1:1, from 1:1 to 5:1, from 5:1 to 10:1, from 10:l to 20:1, from 20:1 to 50:1, from 50:1 to 100:1, from 100:1 to 250:1, from 250:1 to 500:1, from 500:1 to 1000:1, from 1000:1 to 1500:1, from 1500:1 to 2000:1, from 2000:1 to 2500:1, from 2500:1 to 3000:1, from 3000:1 to 3500:1, or any combination of two or more of these ranges.
  • the procatalyst can be utilized to make supported catalyst systems or compositions.
  • the procatalyst and support material are contacted together in an inert hydrocarbon liquid to give a suspension in the inert hydrocarbon liquid, then the suspension is contacted with the activator to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then inert hydrocarbon liquid is removed to give the supported catalyst system.
  • the procatalyst, the activator, or both may be disposed on one or more support materials.
  • the procatalyst may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support materials.
  • the procatalyst, the activator, or both may be combined with one or more support materials using one of the support methods well known in the art or as described below.
  • the procatalyst, the activator, or both may be in a supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more support materials.
  • the activator and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported activator in the inert hydrocarbon liquid, then the suspension is contacted with the procatalyst to give a suspension 86021-WO-PCT/DOW 86021 WO of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.
  • support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • Suitable support materials such as inorganic oxides, include oxides of metals of Group 2, 3, 4, 5, 13 or 14 of the IUPAC periodic table.
  • support materials include silica, which may include dehydrated silica, fumed silica, alumina (e.g., as described in International Patent Application No.1999/060033), silica-alumina, and mixtures of these.
  • the fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated).
  • the support material is hydrophobic fumed silica, which may be prepared by treating an untreated fumed silica with a treating agent, such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane.
  • a treating agent such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane.
  • support materials include magnesia, titania, zirconia, magnesium chloride (e.g., as described in U.S.
  • Patent No.5,965,47-7 montmorillonite (e.g., as described in European Patent No.0511665), phyllosilicate, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these.
  • combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these.
  • Additional support materials may also include those porous acrylic polymers described in European Patent No. 0 767 184.
  • Other support materials may also include nanocomposites described in International Patent Application No.
  • a support material is fumed silica available under the trade name CABOSIL TS- 610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.
  • the support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 m 2 /g.
  • silica alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 m 2 /g.
  • silicas are commercially available from several sources including the Davison Chemical Division of W.R. Grace and Company, e.g., Davison 952 and Davison 955 products, and PQ Corporation, e.g., ES70 product.
  • the silica may be in the form of spherical particles, which may be obtained by a spray-drying process.
  • MS3050 product is a silica from PQ Corporation that is not spray-dried.
  • the support material has a surface area of from 10 square meters per gram (m 2 /g) to 700 m 2 /g, a pore volume of from 0.1 cubic meters per gram (cm 3 /g) to 4.0 cm 3 /g, and an average particle size of from 5 microns ( ⁇ m) to 500 ⁇ m.
  • the support material has a surface area of from 50 m 2 /g to 500 m 2 /g, a pore volume of from 0.5 cm 3 /g to 3.5 cm 3 /g, and an average particle size of from 10 ⁇ m to 200 ⁇ m.
  • the support material may have a surface area of from 100 m 2 /g to 400 m 2 /g, a pore volume from 0.8 cm 3 /g to 3.0 cm 3 /g, and an average particle size of from 5 ⁇ m to 100 ⁇ m.
  • the average pore size of the support material is typically from 10 Angstroms ( ⁇ ) to 1,000 ⁇ , such as from 50 ⁇ to 500 ⁇ or from 75 ⁇ to 350 ⁇ .
  • the support material may be uncalcined or calcined.
  • the calcined support material is made prior to being contacted with a precatalyst, activator, and/or hydrophobing agent, by heating the support material in air to give a calcined support material.
  • the calcining comprises heating the support material at a peak temperature from 350 °C to 850 °C, alternatively from 400 °C to 800 °C, alternatively from 400 °C to 700 °C, alternatively from 500 °C to 650 °C and for a time period from 2 to 24 hours, alternatively from 4 to 16 hours, alternatively from 8 to 12 hours, alternatively from 1 to 4 hours, thereby making the calcined support material.
  • the supported catalyst system may be produced by spray drying.
  • at least one of the procatalyst, the activator, and the support may be spray dried.
  • a “spray-dried” material refers to a material comprising components that have 86021-WO-PCT/DOW 86021 WO undergone a spray-drying process.
  • spray-drying processes are known in the art and are suitable for forming the spray-dried catalyst systems disclosed herein.
  • a mixture of procatalyst, support, activator, and inert hydrocarbon liquid may be formed.
  • the mixture may then be spray dried to form a spray - dried supported catalyst system.
  • Spray ⁇ drying the mixture removes the inert hydrocarbon solvent to produce spray ⁇ dried particles, though spray ⁇ drying the mixture may not result in complete removal of liquids from the resulting catalyst system. That is, the spray ⁇ dried catalyst system may include residual amounts (i.e., from 1 wt. % to 3 wt. %) of the inert hydrocarbon solvent.
  • An atomizer such as an atomizing nozzle or a centrifugal high speed disc, for example, may be used to create a spray or dispersion of droplets of the composition.
  • the droplets of the composition may then be rapidly dried by contact with an inert drying gas.
  • the inert drying gas may be any gas that is non-reactive under the conditions employed during atomization, such as nitrogen, for example.
  • the inert drying gas may meet the composition at the atomizer, which produces a droplet stream on a continuous basis.
  • Dried particles of the composition may be trapped out of the process in a separator, such as a cyclone, for example, which can separate solids formed from a gaseous mixture of the drying gas, solvent, and other volatile components.
  • spray drying may improve the productivity, efficiency, and/or resulting polymer properties of at least some of the catalyst systems described herein.
  • methods for producing the spray ⁇ dried catalyst system include spray ⁇ drying a mixture comprising an inert hydrocarbon liquid, a support material, and an activator, thereby forming a spray ⁇ dried supported activator, and then contacting the spray ⁇ dried supported activator with an inert hydrocarbon liquid and the procatalyst to make the spray-dried supported catalyst system. Further embodiments include preparing a trim solution comprising the second inert hydrocarbon solvent and the procatalyst and then contacting the trim solution with the spray ⁇ dried supported activator. In embodiments where a spray ⁇ dried supported activator is contacted with an inert hydrocarbon liquid and the procatalyst, the resulting mixture may be added directly, i.e.
  • a polymerization reactor e.g., a gas polymerization reactor
  • a polymerization reactor e.g., a gas polymerization reactor
  • the dried supported catalyst system may be resuspended in an inert hydrocarbon liquid, and the resulting slurry is added to a polymerization reactor.
  • a mixture of the procatalyst, the support, and the activator in an inert hydrocarbon liquid are used without drying.
  • the supported catalyst system in the inert hydrocarbon liquid may be made in-line prior to entry or injection into the gas phase polymerization reactor and is utilized for a polymerization reaction in the reactor directly without a drying or decanting step.
  • contacting a mixture of the procatalyst and an inert hydrocarbon liquid with a supported or spray dried activator particle is performed in-line to a polymerization reactor.
  • the spray-dried catalyst systems disclosed herein may have the form of a free- flowing powder, for instance. After the spray-drying process, the spray-dried catalyst system and a number of known components may be utilized to form a slurry.
  • the spray-dried catalyst system may be utilized with a diluent to form a slurry suitable for use in olefin polymerization, for example.
  • the slurry may be combined with one or more additional catalysts or other known components prior to delivery into a polymerization reactor.
  • a mixture of the procatalyst, the support, and the activator in an inert hydrocarbon liquid are spray-dried to form a spray-dried catalyst system, and the supported catalyst system is contacted with the procatalyst in an inert hydrocarbon liquid, prior to entry or injection into the gas phase polymerization reactor, and is utilized for a polymerization reactor in the reactor directly without a drying or decanting step.
  • the inert hydrocarbon liquid may comprise a mineral oil, a hydrocarbon solvent, or a combination thereof.
  • the second inert hydrocarbon liquid may have the same or a different composition from the first inert hydrocarbon liquid.
  • Polyethylenes [0084]
  • the supported catalyst system of the present disclosure may be utilized to polymerize a single type of olefin, producing a hompolymer.
  • additional 1-alkenes also called alpha-olefins
  • the additional 1-alkene comonomers typically have no more than 8 86021-WO-PCT/DOW 86021 WO carbon atoms.
  • the supported catalyst systems of the present disclosure may be utilized to polymerize ethylene monomer and at least one 1-alkene comonomer.
  • exemplary 1-alkene comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, and 4-methyl-l-pentene.
  • the at least one 1-alkene comonomer may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or, in the alternative, from the group consisting of 1-hexene and 1-octene.
  • the at least one 1-alkene comonomer comprises 1-butene or 1-hexene.
  • the method produces a polyethylene.
  • from 95 – 99.99 wt. % such as from 95 to 96 wt. %, from 96 to 97 wt. %, from 97 to 98 wt. %, from 98 to 99 wt. %, from 99 to 99.5 wt. %, from 99.5 to 99.9 wt. %, or any combination of two or more of these ranges of units of the polyethylene comprise ethylene based on a total weight of the polyethylene, and 0.01-5 wt. %, such as from 0.01 to 0.05 wt. %, from 0.05 to 0.1 wt. %, from 0.1 wt.
  • % to 0.5 wt. % from 0.5 wt. % to 1 wt. %, from 1 wt. % to 2 wt. %, from 2 wt. % to 3 wt. %, from 3 wt. % to 4 wt. %, from 4 wt. % to 5 wt. %, or any combination of two or more of these ranges of units of the polyethylene comprise the at least one C 3 to C8 1-alkene comonomer, based on the total weight of the polyethylene.
  • the polyethylene may have a melt temperature from 125 °C to 140 °C, such as from 125 °C to 130 °C, from 130 °C to 135 °C, from 135 °C to 140 °C, or any combination of two or more of these ranges.
  • the polyethylene may have a melt index (I2) from 0 to 120 dg/min, such as from 0 to 0.1 dg/min, from 0.1 to 0.5 dg/min, from 0.5 to 1 dg/min, from 1 to 5 dg/min, from 5 to 10 dg/min, from 10 to 20 dg/min, from 20 to 50 dg/min, from 50 to 80 dg/min, from 80 to 100 dg/min, from 100 to 120 dg/min, or any combination of two or more of these ranges.
  • Melt index (I2) is measured according to ASTM-1238 Condition B (190 °C, 2.16 kg).
  • the polyethylene may have a melt flow index (I 21 ) from 0 to 2,000 dg/min, such as from 0 to 0.1 dg/min, from 0.1 to 0.5 dg/min, from 0.5 to 1 dg/min, from 1 to 5 dg/min, from 5 to 10 dg/min, from 10 to 20 dg/min, from 20 to 50 dg/min, from 50 to 100 dg/min, from 100 to 500 dg/min, from 500 to 1000 dg/min, from 1000 to 1500 86021-WO-PCT/DOW 86021 WO dg/min, from 1500 to 2000 dg/min, or any combination of two or more of these ranges.
  • a melt flow index (I 21 ) from 0 to 2,000 dg/min, such as from 0 to 0.1 dg/min, from 0.1 to 0.5 dg/min, from 0.5 to 1 dg/min, from 1 to 5 dg/min, from
  • the polyethylenes may further comprise one or more additives.
  • additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof.
  • the ethylene-based polymers may contain any amounts of additives.
  • the polyethylenes may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the polyethylenes and the one or more additives.
  • the polyethylenes may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers.
  • the polyethylenes may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the polyethylenes and all additives or fillers.
  • the polyethylenes may further be blended with one or more polymers to form a blend.
  • the produced polyethylene may be used in a wide variety of products and end-use applications.
  • the produced polyethylene may also be blended and/or co-extruded with any other polymer.
  • Non-limiting examples of other polymers include linear low density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene, polypropylenes, and the like.
  • the produced polyethylene and blends including the produced polyethylene may be used to produce blow-molded components or products, among various other end uses.
  • the produced polyethylene and blends including the produced polyethylene may be useful in forming operations such as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding.
  • Films may include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, and membranes in food-contact and non-food contact applications.
  • Fibers may include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, and geotextiles.
  • Extruded articles may include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles may include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys. 86021-WO-PCT/DOW 86021 WO [0091]
  • TEST METHODS Melt Indices (I2, I5, I21) Melt flow index of polyethylene and copolymers was measured via the rate of extrusion of molten polymers through a die of specified length and diameter, under prescribed conditions of temperature, load, piston position in the barrel and duration. The exper iments are carried out employing a melt indexer and according to method ASTM-1238, Condition B. [0094] Melt index (I2) is measured according to ASTM-1238 Condition B (190 °C, 2.16 kg). Melt index (I5) is measured according to ASTM-1238 Condition B (190 °C, 5 kg).
  • Procatalysts 86021-WO-PCT/DOW 86021 WO [0097] The structures of Procatalysts 1-9 are shown below. Procatalysts 1-9 were synthesized according to the methods described in U.S. Provisional Patent Application Nos. 63/665,659 and 63/665,661, the entirety of both of which is incorporated by reference herein. 86021-WO-PCT/DOW 86021 WO Spray-Dried Catalyst Production [0098] Spray-dried catalyst samples were prepared and sprayed in a nitrogen-purged glove box as follows.
  • Table 1 describes the amounts of the p rocatalyst, fumed silica, 10% MAO solution, and toluene used to make each of the spray - dried catalysts.
  • 86021-WO-PCT/DOW 86021 WO [0099] Supported catalyst samples S-10 through S-15, which may also be referred to as a t rim composition or trim supported catalyst samples, were made as follows. In a nitrogen - purged glove box, supported MAO (SMAO) was added into a 10 mL Parr Bomb, and then anhydrous deoxygenated methylcyclohexane (3.0 mL) was added to create a slurry.
  • SMAO supported MAO
  • the gas phase reactor employed was a 2-liter, stainless steel autoclave equipped with a mechanical agitator.
  • the reactor was first dried, or “baked out,” for 1 hour by charging the reactor with 400 g of NaCl and heating at 105 °C under nitrogen for 60 minutes. After baking out the reactor, 5 g of spray-dried methyl aluminoxane (SDMAO) was introduced as a scavenger under nitrogen pressure. After adding SDMAO, the reactor was sealed, and components were stirred. The reactor was then charged with hydrogen and 1-hexene, and pressurized with ethylene. Once the system reached a steady state, the catalyst was charged into the reactor at 80 °C to start polymerization.
  • SDMAO spray-dried methyl aluminoxane
  • the reactor was brought 86021-WO-PCT/DOW 86021 WO to the indicated reaction temperature and maintained at this temperature, while keeping the ethylene, 1-hexene, and hydrogen feed ratios consistent throughout the 1 hour run.
  • the reactor was cooled down, vented, and opened.
  • the resul ting product mixture was washed with water and methanol, then dried.
  • Polymerization activity or productivity grams polymer/gram catalyst-hour
  • polymerization efficiency grams polymer / gram metal (Ti, Zr or Hf) was determined as the ratio of polymer produced, based on ethylene and hexene uptake/consumption, compared to the amount of catalyst added to the reactor.
  • melt flow ratio MFR, I 21 /I 2
  • DSC melt flow ratio
  • Table 3 86021-WO-PCT/DOW 86021
  • the semi-batch reactor results are for the spray-dried catalysts S-1 through S-9, which are zirconium catalysts that contain differentiated benzothiazoles and non-substituted as well as alkyl-substituted cyclopentadienes.
  • the productivities and/or efficiencies for the catalysts utilized herein are high compared to industrially relevant benchmarks (such as metallocene, Ziegler-Natta, or chromium catalyst systems), with productivities up to 16,200 gPE/gCat/hr and efficiencies up to 3.6 MM gPE/gM.
  • Optimal productivity and efficiency were observed for those catalysts possessing a combination of a 2,6-dimethylphenyl substituted amine-containing benzothiazole and a non-substituted, methyl, propyl, or butyl substituted cyclopentadiene as ligands for the zirconium complex (S-1, S-5, S-7, and S-9).
  • melt flow data I2, I, I21
  • processes utilizing these catalysts are capable of producing ethylene/hexene copolymers with broad melt flow ratios (MFR), with a range of weight average molecular weights (M w ) based on the melt index (I2) and flow index (I21) measurements, and in some instances, with no flow or fractional melt index capability.
  • MFR melt flow ratio
  • M w weight average molecular weights
  • each of these catalysts also produce ethylene/hexene copolymers with high ethylene selectivity, or enchainment, even under prototypical low-density conditions in a gas phase reactor, as compared to industrially relevant benchmarks (Zr- and Hf-metallocene catalyst systems).

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Un procédé de fabrication de polyéthylène comprend la polymérisation, par polymérisation en phase gazeuse, d'un monomère d'éthylène et éventuellement d'au moins un comonomère 1-alcène en C3 à C8 et d'un système catalytique, permettant ainsi de former un polyéthylène. Le système catalytique comprend un procatalyseur ayant une structure selon la formule (I) : Formule (I)
PCT/US2025/034990 2024-06-28 2025-06-24 Procédés de polymérisation en phase gazeuse pour la fabrication de polymère à base d'éthylène à l'aide de systèmes catalytiques contenant des 2-amino-thiazoles Pending WO2026006272A1 (fr)

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US6472484B1 (en) 2000-03-31 2002-10-29 Mitsui Chemicals, Inc. Processes for producing polyolefin composition
WO2020263790A1 (fr) * 2019-06-26 2020-12-30 Dow Global Technologies Llc Catalyseurs de polymérisation d'oléfines portant un thiazole ou un imidazole

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