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US-12617881-B2 - Metallocene compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same

US12617881B2US 12617881 B2US12617881 B2US 12617881B2US-12617881-B2

Abstract

This invention relates to a novel metallocene compound, a catalyst composition comprising the metallocene compound, and a method for preparing olefin polymer using the catalyst composition.

Inventors

  • Minyoung Kang
  • Seyoung Kim
  • Insun Lee
  • Seok Hwan Kim
  • Byung Seok Kim
  • Yoonchul JUNG

Assignees

  • LG CHEM, LTD.

Dates

Publication Date
20260505
Application Date
20211001
Priority Date
20201008

Claims (14)

  1. 1 . A metallocene compound represented by Chemical Formula 1: wherein in Chemical Formula 1, M is Group 4 transition metal, A is carbon or silicon, X 1 and X 2 are each independently, hydrogen, halogen, or substituted or unsubstituted C 1-30 alkyl; R 1 to R 4 are each independently, hydrogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 1-30 alkoxy, substituted or unsubstituted C 2-30 alkoxyalkyl, substituted or unsubstituted C 6-30 aryl, or two adjacent R 1 to R 4 that are bonded to each other to form a substituted or unsubstituted C 5-30 fused ring; R 5 and R 6 are each independently, hydrogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 1-30 alkoxy, substituted or unsubstituted C 2-30 alkoxyalkyl, or substituted or unsubstituted C 6-30 aryl; R 7 and R 8 are each independently, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 1-30 alkoxy, substituted or unsubstituted C 2-30 alkoxyalkyl, substituted or unsubstituted C 6-30 aryl, or R 7 and R 8 that are bonded to each other to form a substituted or unsubstituted C 5-30 spiro ring; R 9 is substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 2-30 alkenyl, C 1-30 alkoxy, substituted or unsubstituted C 2-30 alkoxyalkyl, or substituted or unsubstituted C 6-30 aryl; each R 10 is independently, hydrogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 1-30 alkoxy, substituted or unsubstituted C 2-30 alkoxyalkyl, substituted or unsubstituted C 6-30 aryl, or two adjacent R 10 that are bonded to each other to form a substituted or unsubstituted C 5-30 fused ring, R 11 is hydrogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 2-30 alkenyl, C 1-30 alkoxy, substituted or unsubstituted C 2-30 alkoxyalkyl, or substituted or unsubstituted C 6-30 aryl, m is an integer of 1 to 4, n is an integer of 1 to 3, and k is 0 or 1.
  2. 2 . The metallocene compound according to claim 1 , wherein the metallocene compound represented by Chemical Formula 1 is represented by Chemical Formula 1-1 or 1-2: wherein in Formulas 1-1 and 1-2, M, X 1 , X 2 , A, R 1 to R 11 , m and n are as defined in claim 1 .
  3. 3 . The metallocene compound according to claim 1 , wherein M is zirconium (Zr) or hafnium (Hf).
  4. 4 . The metallocene compound according to claim 1 , wherein X 1 and X 2 are each independently, chloro (Cl), or C 1-5 alkyl.
  5. 5 . The metallocene compound according to claim 1 , wherein R 1 to R 4 are each independently, hydrogen, C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkoxyalkyl, or two adjacent R 1 to R 4 together forming a fused ring selected from the group consisting of the following formulae, and if there are two fused rings, they are identical to or different from each other: wherein, each R′ is independently, C 1-10 alkyl, substituted or unsubstituted phenyl, 9-(C 1-10 alkyl)-9H-carbazolyl, 9-(C 2-10 alkoxyalkyl)-9H-carbazolyl or 9-phenyl-9H-carbazolyl, R″ is C 1-10 alkyl, and each o is independently an integer of 0 to 4.
  6. 6 . The metallocene compound according to claim 1 , wherein R 5 and R 6 are each independently, hydrogen, C 1-10 alkyl, C 2-10 alkenyl or C 2-10 alkoxyalkyl.
  7. 7 . The metallocene compound according to claim 1 , wherein R 7 and R 8 are each independently, C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkoxyalkyl, phenyl substituted with C 2-10 alkoxyalkyl or unsubstituted, or spiro C 5-10 cycloalkane formed by bonding of R 7 and R 8 with each other.
  8. 8 . The metallocene compound according to claim 1 , wherein R 9 is C 1-10 alkyl or C 2-10 alkoxyalkyl.
  9. 9 . The metallocene compound according to claim 1 , wherein each R 10 is independently, hydrogen, C 1-10 alkyl or C 2-10 alkoxyalkyl, or two adjacent R 10 together forming a fused cycloalkane ring.
  10. 10 . The metallocene compound according to claim 1 , wherein each R 11 is independently, hydrogen, C 1-10 alkyl or C 2-10 alkoxyalkyl.
  11. 11 . The metallocene compound according to claim 1 , wherein the metallocene compound represented by Chemical Formula 1 is selected from the group consisting of the following compounds:
  12. 12 . A catalyst composition comprising: the metallocene compound according to claim 1 ; a carrier; and one or more cocatalyst compounds selected from the group consisting of compounds represented by Chemical Formula 2 or Chemical Formula 3: —[Al(R 12 )—O] a — [Chemical Formula 2] wherein in Chemical Formula 2, each R 12 is independently halogen, C 1-20 alkyl or C 1-20 haloalkyl; and a is an integer of 2 or more; J(R 13 ) 3 [Chemical Formula 3] wherein in Chemical Formula 3, each R 13 is independently, halogen, C 1-20 alkyl or C 1-20 haloalkyl; and J is aluminum or boron.
  13. 13 . A method for preparing an olefin polymer, comprising polymerizing an olefin monomer, in the presence of the catalyst composition of claim 12 .
  14. 14 . The method for preparing an olefin polymer according to claim 13 , wherein the olefin monomer comprises one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene norbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

Description

CROSS-REFERENCE TO RELATED APPLICATION(S) This application claims the benefit of Korean Patent Application No. 10-2020-0130132 filed on Oct. 8, 2020 with the Korean Intellectual Property Office, the disclosures of which are herein incorporated by reference in their entirety. TECHNICAL FIELD This invention relates to a novel metallocene compound, a catalyst composition comprising the metallocene compound, and a method for preparing an olefin polymer using the catalyst composition. More specifically, this invention relates to a novel metallocene compound that has high activity in a polymerization reaction, and can control the molecular weight and fine structure of prepared olefin-based polymer, a catalyst composition comprising the metallocene compound, and a method for preparing an olefin polymer using the catalyst composition. BACKGROUND ART Olefin polymerization systems are divided into Ziegler Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed corresponding to each characteristic. The Ziegler Natta catalyst has been widely applied in the existing commercial processes since it was invented in the fifties, but since it is a multi-site catalyst with several active sites, it is characterized by wide molecular weight distribution of polymer, and is limited in terms of securing of desired properties due to non-uniform composition distribution of comonomers. Meanwhile, the metallocene catalyst consists of a main catalyst, of which main component is a transition metal compound, and a cocatalyst, which is an organometal compound including aluminum as the main component, and such a catalyst is a homogeneous complex catalyst and a single site catalyst, obtains polymer with narrow molecular weight distribution and uniform comonomer composition distribution according to the properties of the single site catalyst, and can change the stereoregularity, copolymerization property, molecular weight, crystallinity, etc. according to the modification of the ligand structure of the catalyst and change of polymerization conditions. Meanwhile, polyolefin resin for injection molding is required to have excellent long-term durability and processability. High pressure resistance can be generally exhibited in high density polyethylene region, because modulus increases and force withstanding high pressure increases as crystallinity in polyolefin resin is higher. However, if density is high, resistance to brittle fracture may be lowered, and thus, long-term pressure resistance may be lowered. And, if molecular weight is low or molecular weight distribution is narrow, sagging (melt sagging) may be generated during processing of injection molded products, thus rendering processing difficult, and thus, polyolefin resin having high molecular weight and very wide molecular weight distribution should be applied so as to solve the problems. Although methods of controlling molecular weight distribution by synthesizing various supported metallocene catalysts have been developed so as to improve such problems, in case an olefin polymer is prepared using the existing metallocene catalyst, due to insufficient catalyst activity, economic efficiency may be lowered, or molecular weight distribution of prepared polymer may be narrow, thus rendering it difficult to prepare aimed polymer. Thus, there is a continued demand for a method for preparing a metallocene catalyst that has excellent activity, and can easily control the properties of olefin-based polymer. DETAILED DESCRIPTION OF THE INVENTION Technical Problem It is an object of the invention to provide a novel metallocene compound, a catalyst composition comprising the metallocene compound, and a method for preparing an olefin polymer using the catalyst composition. Technical Solution There is provided a metallocene compound represented by the following Chemical Formula 1: in the Chemical Formula 1,M is Group 4 transition metal,A is carbon or silicon,X1 and X2 are each independently, hydrogen, halogen, or substituted or unsubstituted C1-30 alkyl; R1 to R4 are each independently, hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C1-30 alkoxy, substituted or unsubstituted C2-30 alkoxyalkyl, or substituted or unsubstituted C6-30 aryl, and among them, two neighboring substituents may be bonded to each other to form a substituted or unsubstituted C5-30 fused ring;R5 and R6 are each independently, hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C1-30 alkoxy, substituted or unsubstituted C2-30 alkoxyalkyl, or substituted or unsubstituted C6-30 aryl;R7 and R5 are each independently, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C1-30 alkoxy, substituted or unsubstituted C2-30 alkoxyalkyl, or substituted or unsubstituted C6-30 aryl, a