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EP-4737489-A1 - CATALYST COMPOSITION PREPARATION METHOD AND CONJUGATED DIENE-BASED POLYMER PREPARATION METHOD

EP4737489A1EP 4737489 A1EP4737489 A1EP 4737489A1EP-4737489-A1

Abstract

The present invention relates to a method for preparing a catalyst composition for continuously preparing a catalyst composition having improved catalyst activity by pre-treating a hydrogen-bonded lanthanide rare earth element compound and/or an oligomer type of a lanthanide rare earth element compound, which induce the deterioration of the catalyst activity, and a method for preparing a conjugated diene-based polymer using the catalyst composition prepared thereby.

Inventors

  • CHOI, SEO WON
  • LEE, TAE CHUL
  • SOHN, HAE SUNG
  • KIM, DONG HUI
  • JU, Jee Won

Assignees

  • LG CHEM, LTD.

Dates

Publication Date
20260506
Application Date
20240605

Claims (13)

  1. A method for preparing a catalyst composition, the method comprising: a step of performing pre-treatment reaction of a hydrogen bond, an oligomer type, or a combination thereof on a lanthanide rare earth element compound (S10); a step of alkylation of mixing and reacting the lanthanide rare earth element compound of which the hydrogen bond, the oligomer type, or the combination thereof is pretreated in the step (S10), with an alkylating agent (S20); and a step of halogenation of mixing and reacting the alkylated lanthanide rare earth element compound in the step (S20), with a halogen compound (S30), wherein the step (S10) is performed by mixing and reacting the lanthanide rare earth element compound, and one or more trialkyl aluminums selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum, and the step (S10), the step (S20) and the step (S30) are each performed in individual reactors connected in series.
  2. The method for preparing a catalyst composition according to claim 1, wherein the step (S10) is performed before the alkylation of the lanthanide rare earth element compound by the trialkyl aluminum occurs.
  3. The method for preparing a catalyst composition according to claim 1, wherein the lanthanide rare earth element compound is a neodymium compound represented by the following Formula 1: in Formula 1, R 1 to R 3 are each independently hydrogen or an alkyl group of 1 to 12 carbon atoms, where R 1 to R 3 are not all hydrogen.
  4. The method for preparing a catalyst composition according to claim 1, wherein the lanthanide rare earth element compound is one or more selected from the group consisting of Nd(2-ethyl hexanoate) 3 , Nd(2,2-dimethyl decanoate) 3 , Nd(2,2-diethyl decanoate) 3 , Nd(2,2-dipropyl decanoate) 3 , Nd(2,2-dibutyl decanoate) 3 , Nd(2,2-dihexyl decanoate) 3 , Nd(2,2-dioctyl decanoate) 3 , Nd(2-ethyl-2-propyl decanoate) 3 , Nd(2-ethyl-2-butyl decanoate) 3 , Nd(2-ethyl-2-hexyl decanoate) 3 , Nd(2-propyl-2-butyl decanoate) 3 , Nd(2-propyl-2-hexyl decanoate) 3 , Nd(2-propyl-2-isopropyl decanoate) 3 , Nd(2-butyl-2-hexyl decanoate) 3 , Nd(2-hexyl-2-octyl decanoate) 3 , Nd(2,2-diethyl octanoate) 3 , Nd(2,2-dipropyl octanoate) 3 , Nd(2,2-dibutyl octanoate) 3 , Nd(2,2-dihexyl octanoate) 3 , Nd(2-ethyl-2-propyl octanoate) 3 , Nd(2-ethyl-2-hexyl octanoate) 3 , Nd(2,2-diethyl nonanoate) 3 , Nd(2,2-dipropyl nonanoate) 3 , Nd(2,2-dibutyl nonanoate) 3 , Nd(2,2-dihexyl nonanoate) 3 , Nd(2-ethyl-2-propyl nonanoate) 3 , and Nd(2-ethyl-2-hexyl nonanoate) 3 .
  5. The method for preparing a catalyst composition according to claim 1, wherein the alkylating agent is an alkyl aluminum compound represented by the following Formula 2: [Formula 2] AlR 4 R 5 R 6 in Formula 2, R 4 to R 6 are each independently hydrogen or an alkyl group of 1 to 12 carbon atoms, where R 4 to R 6 are not all hydrogen and do not comprise tri-n-hexyl aluminum and tri-n-octyl aluminum.
  6. The method for preparing a catalyst composition according to claim 1, wherein the alkylating agent is a dialkyl aluminum hydride.
  7. The method for preparing a catalyst composition according to claim 1, wherein the pre-treatment reaction in the step (S10), the alkylation in the step (S20), or the pre-treatment reaction in the step (S10) and the alkylation in the step (S20) are performed by including a conjugated diene-based monomer.
  8. The method for preparing a catalyst composition according to claim 1, wherein the halogen compound is one or more selected from the group consisting of an alkyl aluminum halide represented by the following Formula 3 and an alkyl aluminum sesquihalide represented by the following Formula 4: [Formula 3] AlR 7 R 9 R 9 in Formula 3, R 7 to R 9 are each independently a halogen group or an alkyl group of 1 to 12 carbon atoms, where R 7 to R 9 are not all halogen groups, in Formula 4, R 10 to R 12 are each independently an alkyl group of 1 to 12 carbon atoms, and X 1 to X 3 are each independently a halogen group.
  9. The method for preparing a catalyst composition according to claim 1, wherein the halogen compound is one or more selected from the group consisting of a dialkyl aluminum halide and an alkyl aluminum sesquihalide.
  10. The method for preparing a catalyst composition according to claim 1, wherein the step (S20) is continuously performed in multiple reactors connected in series.
  11. The method for preparing a catalyst composition according to claim 10, wherein the alkylating agent is divided and injected into the multiple reactors connected in series.
  12. The method for preparing a catalyst composition according to claim 1, wherein the step (S10), the step (S20) and the step (S30) are continuously performed.
  13. A method for preparing a conjugated diene-based polymer, the method comprising a step of polymerizing a conjugated diene-based monomer in the presence of the catalyst composition prepared by the method for preparing a catalyst composition according to claim 1, in a hydrocarbon solvent to prepare an active polymer (S100).

Description

TECHNICAL FIELD [Cross-reference to Related Applications] The present application claims the benefit of priority based on Korean Patent Application No. 10-2023-0082987, filed on June 27, 2023, the entire contents of which are incorporated herein by reference. [Technical Field] The present invention relates to a method for preparing a catalyst composition for preparing a conjugated diene-based polymer, and a method for preparing a conjugated diene-based polymer using the same. BACKGROUND ART Recently, according to the growing attention on saving energy and environmental issues, the decrease of the fuel consumption ratio of cars is required. As a method for accomplishing the requirement, a method for decreasing the molecular weight distribution, while increasing the cis bond content and linearity of polybutadiene in a rubber composition for forming tires has been suggested. Polybutadiene may be prepared using a Ziegler-Natta catalyst, and the Ziegler-Natta catalyst is prepared by activating an organic acid metal compound with an alkyl aluminum and an alkyl aluminum halide compound, and the catalyst prepared is reacted with a 1,3-butadiene monomer to prepare polybutadiene. Here, the organic acid metal compound includes titanium-based, nickel-based, cobalt-based and lanthanum-based compounds, and lanthanide rare earth element compounds are mainly used in view of increasing the cis bond content and linearity and decreasing the molecular weight distribution of polybutadiene. The examples of the lanthanide rare earth element compound include neodymium-based compounds, particularly, neodymium versatate (NdV). The lanthanide rare earth element compound may be activated through alkylation using an alkyl aluminum compound, and then, through halogenations using an alkyl aluminum halide compound, and in order to stabilize a catalyst, a 1,3-butadiene monomer may be injected during the alkylation for preforming. In this case, the lanthanide rare earth element compound such as NdV is not present as a single compound type but is present as a hydrogen-bonded type and/or an oligomer type by humidity and an aliphatic compound used during a preparation process (Non-patent Document 1 and Non-patent Document 2). However, if alkylation is performed with respect to the hydrogen-bonded lanthanide rare earth element compound and/or the oligomer type of the lanthanide rare earth element compound right away, the alkylation takes long time when compared to a case where the lanthanide rare earth element compound is present as a single compound, and there are problems in that the alkylation is insufficiently performed. If such a lanthanide rare earth element compound that has been insufficiently undergone the alkylation is injected into a halogenation reactor for performing the halogenation, it may be a factor of deteriorating catalyst activity and may arise issues of increasing the contamination of a catalyst preparation apparatus. US Registration Patent Publication No. 9056303 (Patent Document 1) discloses a method for manufacturing a catalyst system using multiple alkylation reactors. In case of continuously preparing in order to solve defects during manufacturing a catalyst system in a batch mode, Patent Document 1 particularly specifies the type of reactors, and controlling the output flux of the catalyst system in a line outlet to a required degree to remain in a suitable residual time range for alkylation and chlorination so as to prevent the formation of gel in the reactor and to secure the flexibility of the salt of an alkylating agent and a rare earth element, which may influence the degree of catalyst activity. In addition, Japanese Registration Patent Publication No. 5072191 (Patent Document 2) discloses a method for preparing a catalyst for polymerizing a conjugated diene, including injecting an alkyl aluminum compound and an alkyl aluminum hydride in order. However, in Patent Documents 1 and 2, only alkylation reaction is directly performed with respect to a lanthanide compound during preparing a catalyst system and a catalyst for polymerizing a conjugated diene, but the type of the lanthanide compound injected and influence on catalyst activity thereby are not recognized. [Prior Art Documents] [Patent Documents] (Patent Document 1) US 9056303 B2(Patent Document 2) JP 5072191 B2 [Non-patent Documents] (Non-patent Document 1) "A Highly Reactive and Monomeric Neodymium Catalyst", Macromolecules 2002, 35, 13, 4875-4879 (https://doi.org/10.1021/ma012123p)(Non-patent Document 2) "Living and non-living Ziegler-Natta catalysts: electronic properties of active site", Polymer, Volume 44, Issue 21, October 2003, Pages 6555-6558 (https://doi.org/10.1016/S0032-3861(03)00698-0) DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM The task for solving in the present invention is to improve catalyst activity in continuously preparing a catalyst composition for polymerizing polybutadiene, by pre-treating a hydrogen-bonded lanthanide rare earth ele