Modification initiator and modified conjugated diene-based polymer including the same

Patent metadata

Field	Value
Publication number	US-11773191-B2
Application number	US-202117212192-A
Country	US
Kind code	B2
Filing date	Mar 25, 2021
Priority date	Oct 4, 2016
Publication date	Oct 3, 2023
Grant date	Oct 3, 2023

Abstract

The present invention relates to a modification initiator and a modified conjugated diene-based polymer including the same, and more particularly, the present invention provides a modification initiator including a compound represented by Formula 1, a modified conjugated diene-based polymer including the same, and a method of preparing a modified conjugated diene-based polymer.

First claim

The invention claimed is:

1. A method of preparing a modified conjugated diene-based polymer, the method comprising a step (S1) of preparing an active polymer coupled with an alkali metal by polymerization of a conjugated diene-based monomer, or an aromatic vinyl-based monomer with a conjugated diene-based monomer in a hydrocarbon solvent which includes a modification initiator including a compound represented by Formula 1:

wherein, in Formula 1,
Y 1 and Y 2 are each independently M or R 15 , wherein Y 2 is R 15 when Y 1 is M, and Y 2 is M when Y 1 is R 15 ,
M is an alkali metal,
R 1 , R 2 , and R 15 are each independently hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms which includes a nitrogen (N), oxygen (O), or sulfur (S) atom; a heteroalkenyl group having 2 to 30 carbon atoms which includes an N, O, or S atom; a heteroalkynyl group having 2 to 30 carbon atoms which includes an N, O, or S atom; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 5 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms which includes at least one of N, O, and S atoms,
R 3 is hydrogen,
R 4 is a single bond; an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms; a cycloalkylene group having 5 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms; or an arylene group having 5 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms,
R 5 is an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms which includes an N, O, or S atom; a heteroalkenyl group having 2 to 30 carbon atoms which includes an N, O, or S atom; a heteroalkynyl group having 2 to 30 carbon atoms which includes an N, O, or S atom; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 5 to 30 carbon atoms; a heterocyclic group having 3 to 30 carbon atoms which includes at least one of N, O, and S atoms; a functional group represented by Formula 2; or a functional group represented by Formula 3,
n is an integer selected from 1 to 5, at least one of R 5 is the functional group represented by Formula 2 or 3, and a plurality of R 5 are the same or different from each other when n is an integer selected from 2 to 5,

wherein, in Formulae 2 and 3,
R 6 and R 10 are each independently an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms; a cycloalkylene group having 5 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms; or an arylene group having 5 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms,
R 7 , R 8 , and R 12 are each independently an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 20 carbon atoms,
R 9 , R 11 , R 13 , and R 14 are each independently hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms which includes an N, O, or S atom; a heteroalkenyl group having 2 to 30 carbon atoms which includes an N, O, or S atom; a heteroalkynyl group having 2 to 30 carbon atoms which includes an N, O, or S atom; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 5 to 30 carbon atoms; a heterocyclic group having 3 to 30 carbon atoms which includes at least one of N, O, and S atoms; an alkenyl group having 2 to 30 carbon atoms which is substituted with an alkyl group having 1 to 10 carbon atoms which includes an alkali metal; or an aryl group having 6 to 30 carbon atoms which is substituted with an alkyl group having 1 to 10 carbon atoms which includes an alkali metal,
X 1 and X 2 are each independently one selected from N, O, and S atoms, R 9 is not present when X 1 is an O or S atom, R 14 is not present when X 2 is an O or S atom, and
m is an integer of 1 or 2.

2. The method of claim 1 , wherein the compound represented by Formula 1 is used in an amount of 0.01 mmol to 10 mmol based on total 100 g of the monomer.

3. The method of claim 1 , wherein
in Formula 1,
Y 1 and Y 2 are each independently M or R 15 , wherein Y 2 is R 15 when Y 1 is M, and Y 2 is M when Y 1 is R 15 ,
M is an alkali metal,
R 1 , R 2 , and R 15 are each independently hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; and an alkynyl group having 2 to 30 carbon atoms,
R 3 is hydrogen,
R 4 is a single bond; or an unsubstituted alkylene group having 1 to 20 carbon atoms,
R 5 is an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a functional group represented by Formula 2; or a functional group represented by Formula 3,
n is an integer selected from 1 to 5, at least one of R 5 is the functional group represented by Formula 2 or 3, and a plurality of R 5 are the same or different from each other when n is an integer selected from 2 to 5,
wherein, in Formulae 2 and 3,
R 6 and R 10 are each independently an unsubstituted alkylene group having 1 to 20 carbon atoms,
R 7 , R 8 , and R 12 are each independently an unsubstituted alkylene group having 1 to 20 carbon atoms,
R 9 , R 11 , R 13 , and R 14 are each independently hydrogen; an alkyl group having 1 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 5 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms which is substituted with an alkyl group having 1 to 10 carbon atoms which includes an alkali metal; or an aryl group having 6 to 30 carbon atoms which is substituted with an alkyl group having 1 to 10 carbon atoms which includes an alkali metal,
X 1 and X 2 are each independently an N atom, and
m is an integer of 1 or 2.

4. The method of claim 1 , wherein the compound represented by Formula 1 comprises one selected from the group consisting of compounds represented by Formulae 1-1 to 1-13:

wherein, in Formulae 1-1 to 1-13,
M is an alkali metal,
R 15 is hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; or an alkynyl group having 2

Assignees

• Lg Chemical Ltd

Inventors

• Kim Min Soo
• Lee Soo Yong
• Choi Won Mun

Classifications

• C08C19/42 Primary

  reacting with metals or metal-containing groups · CPC title

• C07F7/08

  Compounds having one or more C—Si linkages · CPC title

• C08C19/25 Primary

  Incorporating silicon atoms into the molecule · CPC title

• C08C19/26

  Incorporating metal atoms into the molecule · CPC title

• C08C19/44

  of polymers containing metal atoms exclusively at one or both ends of the skeleton · CPC title