Search

KR-102962845-B1 - Catalytic system

KR102962845B1KR 102962845 B1KR102962845 B1KR 102962845B1KR-102962845-B1

Abstract

The present invention relates to a catalyst system for producing an ethylene copolymer by a high-temperature solution process, wherein the catalyst system comprises (i) a metallocene complex of a group 4 transition metal comprising one or more ligands selected from optionally substituted cyclopentadienyl (Cp), indenyl (Ind), and fluorenyl (Flu) ligands, and (ii) a solid alkyl aluminum oxide co-catalyst. Furthermore, the present invention relates to a process comprising the preparation of the catalyst system, the use thereof in a high-temperature solution process, and the polymerization of ethylene and a C4-10 alpha-olefin comonomer by a high-temperature solution process in the presence of the catalyst system.

Inventors

  • 레스코니 루이지 마리아 크리스토포로
  • 파이트 안나
  • 사블롱 라파엘
  • 이즈머 브야체슬라프 브이
  • 코노노비치 드미트리 에스
  • 보스코보이니코프 알렉산더 제트

Assignees

  • 보레알리스 게엠베하

Dates

Publication Date
20260511
Application Date
20200409
Priority Date
20190412

Claims (20)

  1. A method for producing an ethylene-C4 - C12 alpha-olefin copolymer comprising polymerizing ethylene and a C4-12 alpha-olefin comonomer by a high temperature solution process at a temperature greater than 100°C in the presence of a catalyst system, wherein the catalyst system (i) a metallocene complex of a group 4 transition metal comprising one or more ligands selected from optionally substituted cyclopentadienyl (Cp), indenyl (Ind), and fluorenyl (Flu) ligands, and (ii) a solid alkyl alumonic acid co-catalyst provided as a suspension in an aliphatic C5 to C24 hydrocarbon solvent or a mixture of said aliphatic hydrocarbon solvents A method for preparing an ethylene- C4 - C12 alpha-olefin copolymer comprising
  2. In paragraph 1, A method for preparing an ethylene- C4 - C12 alpha-olefin copolymer, wherein the metallocene complex in (i) is of the following chemical formula (A) or (B): In the above formula, Z is a ligand coordinating to Mt, and Mt is Ti, Zr, Hf, or a mixture of Zr and Hf, and the mixture of Zr and Hf is a mixture of the complex of formula (A) and the Zr or Hf metal, or a mixture of the complex of formula (B) and the Zr or Hf metal, and X is a sigma ligand, and L is a covalent bridge connecting ligands, and R1 to R5 are independently saturated or unsaturated, linear, branched or cyclic C1- C10 hydrocarbyl groups, C6 -C10 aryl groups, C6 - C20 alkylaryl groups or C6 - C20 arylalkyl groups containing a hydrogen atom, optionally one or two heteroatoms or silicon atoms, or Two adjacent groups R1 to R5 can form a ring comprising 4 to 8 ring atoms, and the atoms that are part of the formed ring may be substituted by one or more R12 groups selected from saturated or unsaturated, linear or branched C1 - C10 hydrocarbyl, C5 - C10 aromatic groups, C6 - C20 alkylaryl or C6 - C20 arylalkyl groups, optionally containing 1 or 2 heteroatoms or silicon atoms.
  3. In paragraph 1, A method for preparing an ethylene- C4 - C12 alpha-olefin copolymer, wherein the metallocene complex in (i) is of the following chemical formula (A) or (B): In the above formula, Z is a ligand coordinating to Mt, and Mt is Ti, Zr, Hf, or a mixture of Zr and Hf, and the mixture of Zr and Hf is a mixture of the complex of formula (A) and the Zr or Hf metal, or a mixture of the complex of formula (B) and the Zr or Hf metal, and X is a sigma ligand, and L is a covalent bridge connecting ligands, and R1 to R5 are independently hydrogen atoms, saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl groups, C6 - C10 aryl groups, C6 - C20 alkylaryl groups, or C6 - C20 arylalkyl groups, wherein two or fewer C atoms of the aryl ring(s) may be replaced by two or fewer heteroatoms, which optionally retain substituents attached to their ring atoms, and such substituents optionally contain one or two heteroatoms or silicon atoms, or Two adjacent groups among R1 to R5 can form a ring comprising 4 to 8 ring atoms, and the atoms that are part of the formed ring may be substituted by one or more R12 groups selected from saturated or unsaturated, linear or branched C1 - C10 hydrocarbyl, C5 - C10 aromatic groups, C6 - C20 alkylaryl or C6 - C20 arylalkyl groups, optionally containing 1 or 2 heteroatoms or silicon atoms.
  4. In paragraph 1, A method for preparing an ethylene- C4 - C12 alpha-olefin copolymer in which the metallocene complex in (i) is of the following chemical formula (I): (I) In the above formula, Mt is Zr, Hf, or a mixture of Hf and Zr, wherein the mixture of Hf and Zr is a mixture of the complex of formula (I) and the metal Zr or Hf, and X is a sigma ligand, and Y is a bridge of the chemical formula -WR y 2- , and n is 1, 2, or 3, and W is C or Si, and Each R y is independently a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl group, C6 - C10 aryl, C6 - C20 alkylaryl group or C6 - C20 arylalkyl group [any one of these optionally contains 1 or 2 heteroatoms or silicon atoms], or It is a heteroatom-containing saturated or unsaturated ring of 3 to 7 ring atoms optionally substituted with linear, branched, or cyclic saturated or unsaturated C1 to C20 hydrocarbyl groups, and R2 to R5 and R2 ' to R5' are independently saturated or unsaturated, linear, branched, or cyclic C1 - C10 hydrocarbon groups, C6 - C10 aryl, C6 - C20 alkylaryl, or C6 -C20 arylalkyl groups containing hydrogen, or optionally one or two heteroatoms or silicon atoms, or Any two adjacent groups among R2 to R5 and/or R2 ' to R5' may form a ring comprising 4 to 8 ring atoms, and an atom that is part of the formed ring may be further substituted by one or more R12 groups selected from saturated or unsaturated, linear or branched C1 - C10 hydrocarbyl, C5 - C10 aromatic groups, C6 - C20 alkylaryl or C6 - C20 arylalkyl groups, which may optionally contain 1 or 2 heteroatoms or silicon atoms, or R2 to R5 and R2 ' to R5' are independently hydrogen atoms, saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl groups, C6 - C10 aryl groups, C6 - C20 alkylaryl groups, or C6 - C20 arylalkyl groups, wherein two or fewer C atoms of the aryl ring(s) may be replaced by two or fewer heteroatoms, which optionally retain substituents attached to their ring atoms, and such substituents optionally contain one or two heteroatoms or silicon atoms, or Two adjacent groups among R2 to R5 and/or R2 ' to R5 ' may form a ring comprising 4 to 8 ring atoms, and an atom that is part of the formed ring may be substituted by one or more R12 groups selected from saturated or unsaturated, linear or branched C1 - C10 hydrocarbyl, C5 - C10 aromatic groups, C6 - C20 alkylaryl or C6 - C20 arylalkyl groups, optionally containing 1 or 2 heteroatoms or silicon atoms, and Each X can be the same or different and is a sigma ligand.
  5. In paragraph 4, A method for preparing an ethylene- C4- C12 alpha -olefin copolymer , wherein each X may be the same or different and is a hydrogen atom, a halogen atom, an R14, OR14, OSO2CF3, OCOR14, SR14, NR142 , or PR142 group [ wherein R14 is a linear or branched, cyclic or acyclic, C1 - C20 -alkyl, C2 - C20 -alkenyl, C2 - C20 -alkynyl, C6 - C20 -aryl, C7 - C20 -alkylaryl, or C7 - C20 - arylalkyl group optionally containing one or more heteroatoms belonging to group 15 or 16 ], or SiR143 , SiHR142 , or SiH2R14 .
  6. In paragraph 4, A method for preparing an ethylene- C4 - C12 alpha-olefin copolymer, wherein each X is independently a halogen atom, an R14 or OR14 group, and R14 is a C1-6 -alkyl, phenyl or benzyl group.
  7. In paragraph 4, A method for preparing an ethylene- C4 - C12 alpha-olefin copolymer, where each X is a methyl, chloro, or benzyl derivative.
  8. In paragraph 1, A method for preparing an ethylene- C4 - C12 alpha-olefin copolymer in which the metallocene complex in (i) is of the following chemical formula (II): (II) In the above formula, Mt is Zr, Hf, or a mixture of Hf and Zr, wherein the mixture of Hf and Zr is a mixture of the complex of formula (II) and the metal Zr or Hf, and Y is a bridge of the chemical formula -WR y 2- , and n is 1, 2, or 3, and W is C or Si, and Each R y is independently a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl group, C6 - C10 aryl, C6 - C20 alkylaryl group or C6 - C20 arylalkyl group [any one of these optionally contains 1 or 2 heteroatoms or silicon atoms], or It is a heteroatom-containing saturated or unsaturated ring of 3 to 7 ring atoms optionally substituted with linear, branched, or cyclic saturated or unsaturated C1 to C20 hydrocarbyl groups, and Each X is a sigma ligand, and R2 to R11 are independently hydrogen, or optionally saturated or unsaturated, linear, branched, or cyclic C1 - C10 hydrocarbon groups, C6 - C10 aryl, C6 - C20 alkylaryl groups, or C6 - C20 arylalkyl groups containing two or fewer heteroatoms or silicon atoms, or Any two adjacent groups among R2 to R11 may form a ring comprising 4 to 8 atoms, and an atom that is part of the formed ring may be further substituted by one or more R12 groups selected from saturated or unsaturated, linear or branched C1 - C10 hydrocarbyl, C5 - C10 aromatic groups, C6 - C20 alkylaryl or C6 - C20 arylalkyl groups, which may optionally contain two or fewer heteroatoms or silicon atoms, or R2 to R11 are independently hydrogen atoms, saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl groups, C6 - C10 aryl groups, C6 - C20 alkylaryl groups, or C6 - C20 arylalkyl groups, wherein two or fewer C atoms of the aryl ring(s) may be replaced by two or fewer heteroatoms, which optionally retain substituents attached to their ring atoms, and such substituents optionally contain one or two heteroatoms or silicon atoms, or Two adjacent groups among R2 to R11 may form a ring comprising 4 to 8 ring atoms, and an atom that is part of the formed ring may be substituted by one or more R12 groups selected from saturated or unsaturated, linear or branched C1 - C10 hydrocarbyl, C5 - C10 aromatic groups, C6 - C20 alkylaryl or C6 - C20 arylalkyl groups, optionally containing 1 or 2 heteroatoms or silicon atoms.
  9. As a catalyst system for producing ethylene copolymers by a high-temperature solution process at a temperature exceeding 100℃, (i) Metallocene complex of the following chemical formula (II): (II) In the above formula, Mt is Zr, Hf, or a mixture of Hf and Zr, wherein the mixture of Hf and Zr is a mixture of the complex of formula (II) and the metal Zr or Hf, and Y is a bridge of the chemical formula -WR y 2- , and n is 1, 2, or 3, and W is C or Si, and Each R y is independently a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl group, C6 - C10 aryl, C6 - C20 alkylaryl group or C6 - C20 arylalkyl group [any one of these optionally contains 1 or 2 heteroatoms or silicon atoms], or It is a heteroatom-containing saturated or unsaturated ring of 3 to 7 ring atoms optionally substituted with linear, branched, or cyclic saturated or unsaturated C1 to C20 hydrocarbyl groups, and Each X is a sigma ligand, and R2 to R11 are independently hydrogen, or optionally saturated or unsaturated, linear, branched, or cyclic C1 - C10 hydrocarbon groups, C6 - C10 aryl, C6 - C20 alkylaryl, or C6 - C20 arylalkyl groups containing two or fewer heteroatoms or silicon atoms, or R2 to R11 are independently hydrogen atoms, saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl groups, C6 - C10 aryl groups, C6 - C20 alkylaryl groups or C6 - C20 arylalkyl groups, wherein two or fewer C atoms of the aryl ring(s) may be replaced by two or fewer heteroatoms, which optionally retain substituents attached to their ring atoms, and such substituents optionally contain one or two heteroatoms or silicon atoms; and (ii) a solid alkyl alumonic acid co-catalyst provided as a suspension in an aliphatic C5 to C24 hydrocarbon solvent or a mixture of said aliphatic hydrocarbon solvents A catalyst system comprising
  10. In Paragraph 9, A catalytic system in which the metallocene complex in (i) is of the following chemical formula (V): (V) In the above formula, Mt is Zr, Hf, or a mixture of Hf and Zr, wherein the mixture of Hf and Zr is a mixture of a complex of formula (V) and a Zr or Hf metal, and Y is a bridge of the chemical formula -WR y 2- , and W is C or Si, and Each R y is independently a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl group, C6 - C10 aryl, C6 - C20 alkylaryl group or C6 - C20 arylalkyl group [any one of these optionally contains 1 or 2 heteroatoms or silicon atoms], or It is a heteroatom-containing saturated or unsaturated ring of 3 to 7 ring atoms optionally substituted with linear, branched, or cyclic saturated or unsaturated C1 to C20 hydrocarbyl groups, and Each X is a sigma ligand, and R6 and R11 are independently saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbon groups, C6- C10 aryl, C6 -C20 alkylaryl or C6 - C20 arylalkyl groups containing hydrogen, or optionally two or fewer heteroatoms or silicon atoms, or R6 and R11 are independently hydrogen atoms, saturated or unsaturated, linear, branched or cyclic C1 - C10 hydrocarbyl groups, C6 - C10 aryl groups, C6 - C20 alkylaryl groups or C6 - C20 arylalkyl groups, wherein two or fewer C atoms of the aryl ring(s) may be replaced by two or fewer heteroatoms, which optionally have substituents attached to their ring atoms, and such substituents optionally contain one or two heteroatoms or silicon atoms.
  11. In Paragraph 9, Each X may be the same or different and is a hydrogen atom, a halogen atom, an R 14 , OR 14 , OSO 2 CF 3 , OCOR 14 , SR 14 , NR 14 2 , or PR 14 2 group [wherein R 14 is a linear or branched, cyclic or acyclic, C 1 -C 20-alkyl, C 2-C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 20 -aryl, C 7 -C 20 -alkylaryl or C 7 -C 20 -arylalkyl group optionally containing one or more heteroatoms belonging to group 15 or 16 ], or a catalyst system, which is SiR 14 3 , SiHR 14 2 , or SiH 2 R 14 .
  12. In Paragraph 9, A catalytic system in which each X is independently a halogen atom, R 14 or OR 14 group, wherein R 14 is a C 1-6 -alkyl, phenyl, or benzyl group.
  13. In Paragraph 9, Each X is a catalytic system, derived from methyl, chloro, or benzyl.
  14. In Paragraph 9, A catalyst system in which a solid alkyl alumonic acid co-catalyst (ii) is a solid alkyl alumonic acid (AlkAO) in which the alkyl group is C1 to C6 alkyl.
  15. In Paragraph 9, A catalyst system in which the above co-catalyst is solid methylalumonic acid (MAO).
  16. In paragraph 15, A catalyst system in which the Al content of the solid MAO is in the range of 25 to 60 weight%.
  17. In Paragraph 9, A catalyst system in which the above-mentioned solid alkyl alumonic acid co-catalyst is provided as a suspension in one or more aliphatic C6 to C12 hydrocarbon solvents.
  18. In Paragraph 9, A catalyst system in which the average particle size of the solid alkyl alumonic acid co-catalyst in the above suspension is in the range of 2 to 20 μm.
  19. In Paragraph 9, A catalyst system in which the content of solid AlkAO in the above suspension is in the range of 3 to 30 weight%.
  20. a) a step of providing a solid alkyl alumonic acid co-catalyst as a suspension in one or more liquid C5 to C24 aliphatic hydrocarbon solvents, b) a step of contacting the suspension of step a) with a metallocene complex of formula (II) in solid form, c) a step of stirring the above suspension for at least 2 hours, and d) a step of obtaining the product in the form of a slurry of an alkyl alumonic acid-supported solid catalyst. A method for manufacturing a catalyst system according to claim 9, comprising

Description

Catalytic system The present invention relates to a novel catalyst system capable of producing polyethylene copolymers by a high-temperature solution polymerization process. The novel catalyst system comprises a substituted cross-linked metallocene complex of a group 4 transition metal and a specific co-catalyst in solid form. This combination produces a catalyst system with significantly improved balance of productivity, comonomer incorporation capability, and molecular weight capability. Metallocene catalysts have been used for decades to manufacture polyolefins. Numerous academic publications and patent applications describe the use of these catalysts in olefin polymerization. Metallocenes are currently used industrially, and polypropylene, as well as polyethylene, is often produced using cyclopentadienyl-based catalyst systems with different substitution patterns. Some of these metallocene catalysts are described in several patent documents as being used in solution polymerization for the production of polyethylene homopolymers or copolymers. For example, WO 2000024792 describes a catalytic system comprising: i) one or more unsubstituted cyclopentadienyl ligands or aromatic fusion-ring substituted cyclopentadienyl ligands; ii) one substituted or unsubstituted aromatic fusion-ring substituted cyclopentadienyl ligand; and iii) a hafnocene catalytic complex derived from a biscyclopentadienyl hafnium organometallic compound having a covalent bridge connecting the two cyclopentadienyl ligands. This bridge may be a single carbon substituted with two aryl groups, each of which is substituted with a C1 -C20 hydrocarbyl or hydrocarbylsilyl group, and one or more of these substituents are linear C3 or higher substituents. Additionally, the catalyst system comprises an activating co-catalyst, which is a precursor ionic compound comprising a halogenated tetraaryl-substituted Group 13 anion, typically a perfluorinated borate compound, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate used in all examples. In addition, many academic papers disclose the effect of ligand structure on high-temperature ethylene homopolymerization and copolymerization by various Cp-Flu metallocenes. Perfluorinated borate activators for single-site catalysts are widely used, particularly in high-temperature solution polymerization, and have been shown to provide satisfactory performance in polymerization. However, these activators have very low solubility in aliphatic hydrocarbons and must be dissolved in aromatic solvents or slurried in aliphatic solvents to be supplied to the polymerization process. Both solutions have disadvantages: aromatic solvents are undesirable in the process due to toxicity, and solid slurries require a stoichiometric ratio of activator to metallocene complexes, resulting in the waste of expensive components. Similarly, metallocene complexes must also have relatively high solubility among aliphatic hydrocarbons. There are commercial activators used with single-site catalysts, which are based on methylalumonic acid (MAO) or mixtures thereof with aluminum alkyl, such as MAO/triisobutylaluminum (MAO/TIBA), modified MAO (MMAO), etc., that is, they are based on perfluorinated borate. If a metallocene/MAO-based catalyst system can be made without aromatic solvents such as toluene, it would be a desirable potential replacement for the currently used metallocene/borate system. The advantage of using an activated metallocene/MAO catalyst system is that complexes with lower solubility in aliphatic hydrocarbons can also be used because solubility is provided by the solvating power of MAO itself. However, while MAO is commercially available in toluene solution, toluene-free MMAO is less efficient at activating these low-solubility complexes. Therefore, there is a need to find a new solution for catalyst activation. Accordingly, the object of the present invention is to provide a metallocene-based catalyst system comprising a metallocene complex and a co-catalyst, wherein the solubility of the metallocene is not a limiting feature for using such a catalyst system in a high-temperature solution process. Accordingly, the object of the present invention is to provide a novel catalyst system that does not require an aromatic solvent. In addition, the objective of the present invention is to provide a metallocene catalyst system in which productivity is maintained at a good level without using fluorinated borate as an activator, or is improved without using such borate as an activator. Another objective of the present invention is to provide a metallocene catalyst system capable of producing a polyethylene polymer by a high-temperature solution process with an improved balance of molecular weight capability and comonomer incorporation capability. In addition, the object of the present invention is to provide a method for manufacturing a catalyst system as described in this specification. In addition, the object of th