Modified conjugated diene-based polymer and method of preparing the same
The present invention relates to a modifier represented by Formula 1, a method of preparing the same, a modified conjugated diene-based polymer having a high modification ratio which includes a modifier-derived functional group, and a method of preparing the polymer.
1. A modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by Formula 1:
wherein, in Formula 1,
R 1 , R 4 , and R 5 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms,
R 2 is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 3 is a connecting group represented by Formula 2 or Formula 3,
wherein, in Formula 2 or Formula 3,
R 6 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms; or a substituent represented by Formula 2-1,
R 7 is a divalent hydrocarbon group having 1 to 20 carbon atoms which unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 8 to R 10 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms,
wherein, in Formula 2-1,
R 11 is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 12 and R 13 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms.
2. The modified conjugated diene-based polymer of claim 1 , wherein the modifier represented by Formula 1 comprises compounds represented by Formulae 1-1 to 1-5:
3. The modified conjugated diene-based polymer of claim 1 , wherein the polymer has a number-average molecular weight of 100,000 g/mol to 700,000 g/mol.
4. The modified conjugated diene-based polymer of claim 1 , wherein the polymer has a molecular weight distribution (Mw/Mn) of 1.05 to 5.
5. The modified conjugated diene-based polymer of claim 1 , wherein the polymer has a S/R (stress/relaxation) value at 100° C. of 0.7 or more.
6. A method of preparing the modified conjugated diene-based polymer of claim 1 , the method comprising:
(1) preparing an active polymer coupled with an organometal by polymerization of a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a catalyst composition including a lanthanide rare earth element-containing compound; and
(2) reacting the active polymer with a modifier represented by Formula 1:
wherein, in Formula 1,
R 1 , R 4 , and R 5 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms,
R 2 is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 3 is a connecting group represented by Formula 2 or Formula 3,
wherein, in Formula 2 or Formula 3,
R 6 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms; or a substituent represented by Formula 2-1,
R 7 is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 8 to R 10 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms,
wherein, in Formula 2-1,
R 11 is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 12 and R 13 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms.
7. The method of claim 6 , wherein the catalyst composition is used in an amount such that the lanthanide rare earth element-containing compound is included in an amount of 0.1 mmol to 0.5 mmol based on 100 g of the conjugated diene-based monomer.
8. The method of claim 6 , wherein the lanthanide rare earth element-containing compound comprises a neodymium compound represented by Formula 7:
wherein, in Formula 7,
R a to R c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, but not all of R a to R c are not hydrogen at the same time.
9. The method of claim 6 , wherein the modifier is used in an amount of 0.5 mol to 20 mol based on 1 mol of the lanthanide rare earth element-containing compound.