Modified conjugated diene-based polymer and method of preparing the same

Patent metadata

Field	Value
Publication number	US-11230618-B2
Application number	US-201716083700-A
Country	US
Kind code	B2
Filing date	Oct 31, 2017
Priority date	Nov 1, 2016
Publication date	Jan 25, 2022
Grant date	Jan 25, 2022

Abstract

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.

First claim

The invention claimed is:

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.

Assignees

• Lg Chemical Ltd

Inventors

• Kim Ji Eun
• Lim Won Taeck
• Choi Won Mun
• Joe Dae June

Classifications

• C07D295/15 Primary

  to an acyclic saturated chain · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08K5/3442

  having two nitrogen atoms in the ring · CPC title

• C08K5/3462

  Six-membered rings · CPC title

• C08L15/00

  Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) · CPC title