Method for preparing catalyst for polymerizing conjugated diene, catalyst and method for preparing conjugated diene-based polymer using the same
A method for preparing a catalyst for use in polymerizing a conjugated diene-based monomer, the catalyst, and a method for preparing a conjugated diene-based polymer using the same are disclosed herein. In an embodiment, a method of preparing a catalyst comprises mixing a lanthanide rare earth element-containing compound, an alkylating agent compound and a halogen compound in the presence of a solvent to prepare a catalyst composition, adding a conjugated diene-based monomer to the catalyst composition to form a preformed catalyst composition, and aging the preformed catalyst composition at a temperature of −1° C. to −15° C. for 3 hours to 98 hours to prepare the catalyst. The catalyst has excellent catalyst activity and polymerization reactivity and is useful for preparing a conjugated diene-based polymer which has an excellent modification ratio and improved compounding properties.
1. A method for preparing a conjugated diene-based polymer, the method consisting of:
mixing a lanthanide rare earth element-containing compound, an alkylating agent compound and a halogen compound in the presence of a non-polar hydrocarbon-based solvent to prepare a catalyst composition;
adding a first conjugated diene-based monomer to the catalyst composition to form a preformed catalyst composition; and
aging the preformed catalyst composition at a temperature of −8° C. to −12° C. for 17 hours to 20 hours to prepare the catalyst,
polymerizing a second conjugated diene-based monomer in the presence of the catalyst, and
adding a modifier and performing a modification reaction.
2. The method according to claim 1 , wherein the aging step is performed under nitrogen (N 2 ) conditions.
3. The method according to claim 1 , wherein the lanthanide rare earth element-containing compound comprises a neodymium compound represented by the following Formula 1:
in Formula 1, R 1 to R 3 are each independently a hydrogen atom, or a linear or branched alkyl group of 1 to 12 carbon atoms.
4. The method according to claim 3 , where R 1 is a linear or branched alkyl group of 6 to 12 carbon atoms, and R 2 and R 3 are each independently a hydrogen atom or a linear or branched alkyl group of 2 to 8 carbon atoms, but R 2 and R 3 are not hydrogen atoms at the same time.
5. The method according to claim 1 , wherein the alkylating agent compound comprises an organoaluminum compound represented by the following Formula 2:
[Formula 2]
Al(R) z (X) 3-z [Formula 2]
in Formula 2,
R is each independently a hydrocarbyl group; or a heterohydrocarbyl group comprising at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, a boron atom, a silicon atom, a sulfur atom and a phosphor atom in a hydrocarbyl group,
X is each independently selected from the group consisting of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy group and an aryloxy group, and
z is an integer of 1 to 3.
6. The method according to claim 1 , wherein the halogen compound comprises any one selected from the group consisting of a diatomic halogen, an interhalogen compound, a hydrogen halide, an organic halide, a nonmetal halide, a metal halide, an organometal halide, and mixtures thereof.
7. The method according to claim 1 , wherein the mixing step is performed at 10° C. to 30° C.
8. The method according to claim 1 , wherein 5 to 20 mol of the alkylating agent compound, 2 to 6 mol of the halogen compound and 100 to 1,000 mol of the solvent are used with respect to 1 mol of the lanthanide rare earth element-containing compound.
9. The method according to claim 1 , wherein the modifier is ethyl 1-(trimethylsilyl)piperidine-4-carboxylate or (E)-N,N-dimethyl-4-((undecylimino)methyl)benzenamine.