Anionic polymerization initiator having anionic terminal comprising amine group, production method for modified conjugated diene-based copolymer using same, and rubber composition comprising modified conjugated diene-based copolymer produced in accordance therewith

Patent metadata

Field	Value
Publication number	US-2016347877-A1
Application number	US-201515117080-A
Country	US
Kind code	A1
Filing date	Nov 20, 2015
Priority date	Dec 1, 2014
Publication date	Dec 1, 2016
Grant date	—

Abstract

Disclosed are an anionic polymerization initiator, which is an organo-alkali metal compound having an anionic end including an amine group, a method of preparing a modified conjugated diene-based polymer using the same, and a rubber composition including the modified conjugated diene-based polymer prepared thereby.

First claim

1 . A modified conjugated diene-based polymer represented by any one of Chemical Formulas 1 to 3 below:

in Chemical Formula 1, R 1 is a C1-C10 alkyl or alkylsilyl group, R 2 is a C1-C10 alkylene or alkylsilylene group, R 3 and R 4 are each a C1-C10 alkyl group, P is a conjugated diene-based polymer chain, X is a substituent represented by Chemical Formula 8 below, a is 0, 1, or 2, b is 1, 2, or 3, a+b is 1, 2, or 3, n is an integer of 0 to 2, and two R 1 s, which are linked with nitrogen, are identical to or different from each other when n is 2, and R 2 , R 3 and R 4 are identical to or different from each other when 3-n is 2 or more;

in Chemical Formula 2, R 1 is a C1-C10 alkyl or alkylsilyl group, R 2 and R 3 are each a C1-C10 alkyl group, P is a conjugated diene-based polymer chain, X is a substituent represented by Chemical Formula 8 below, a is an integer of 1 or 2, b is 1, 2, or 3, a+b is 1 or 2, n is an integer of 0 to 2, and two R 1 s, which are linked with nitrogen, are identical to or different from each other when n is 2, and R 2 and R 3 are identical to or different from each other when 3-n is 2 or more;

in Chemical Formula 3, A is an amine-containing functional group, P is a conjugated diene-based polymer chain, X is a substituent represented by Chemical Formula 8 below, a and b are each independently 1, 2, or 3, R 1 , R 2 and R 3 are each a C1-C10 alkylene or alkylsilylene group, and R 4 and R 5 are identical to or different from each other and are each a C1-C10 alkyl group; and

in Chemical Formula 8, R 1 and R 2 are each independently a C1-C20 alkyl group, R 3 is a C1-C10 alkylene group, R 4 and R 5 are each independently a C1-C10 alkyl group, R 1 and R 2 are linked with each other to form a ring structure, and * represents a bonding position.

2 . A method of preparing a modified conjugated diene-based polymer, comprising:
a) polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer using a hydrocarbon solvent in presence of a compound represented by Chemical Formula 4 below, thus forming an active polymer having an alkali metal end; and b) modifying the active polymer having the alkali metal end with a compound represented by Chemical Formula 5, 6 or 7 below:

in Chemical Formula 4, R 1 and R 2 are each independently a C1-C20 alkyl group, R 3 is a C1-C10 alkylene group, R 4 and R 5 are each independently a C1-C10 alkyl group, M is an alkali metal, and R 1 and R 2 are linked with each other to form a ring structure;

in Chemical Formula 5, R 1 is a C1-C10 alkyl or alkylsilyl group, R 2 is a C1-C10 alkylene or alkylsilylene group, R 3 and R 4 are each a C1-C10 alkyl group, a is an integer of 1 to 3, n is an integer of 0 to 2, and two R 1 s, which are linked with nitrogen, are identical to or different from each other when n is 2, and R 2 , R 3 and R 4 are identical to or different from each other when 3-n is 2 or more;

in Chemical Formula 6, R 1 is a C1-C10 alkyl or alkylsilyl group, R 2 and R 3 are each a C1-C10 alkyl group, a is an integer of 1 or 2, n is an integer of 0 to 2, and two R 1 s, which are linked with nitrogen, are identical to or different from each other when n is 2, and R 2 and R 3 are identical to or different from each other when 3-n is 2 or more; and

in Chemical Formula 7, A is an amine-containing functional group, R 1 , R 2 and R 3 are each a C1-C10 alkylene or alkylsilylene group, and R 4 and R 5 are identical to or different from each other and are each a C1-C10 alkyl group.

3 . The method of claim 2 , wherein the compound represented by Chemical Formula 4 is used in an amount of 0.01 to 10 mmol based on 100 g in total of the monomer.

4 . The method of claim 2 , wherein a molar ratio of the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5, 6 or 7 is 1:0.1 to 1:10.

5 . The method of claim 2 , wherein the polymerizing in a) is performed with additional use of a polar additive.

6 . The method of claim 5 , wherein the polar additive is added in an amount of 0.001 to 10 g based on 1 mmol in total of the compound represented by Chemical Formula 4.

7 . The method of claim 2 , wherein the modified conjugated diene-based polymer has a number average molecular weight (Mn) of 1,000 to 2,000,000 g/mol.

8 . The method of claim 2 , wherein the modified conjugated diene-based polymer includes 0.0001 to 50 wt % of the aromatic vinyl monomer based on 100 wt % in total of the conjugated diene monomer and the aromatic vinyl monomer.

9 . An anionic polymerization initiator, which is a compound represented by Chemical Formula 4 below:

in Chemical Formula 4, R 1 and R 2 are each independently a C1-C20 alkyl group, R 3 is a C1-C10 alkylene group, R 4 and R 5 are each independently a C1-C10 alkyl group, M is an alkali metal, and R 1 and R 2 are linked with each other to form a ring structure.

10 . The anionic polymerization initiator of claim 9 , wherein the compound represented by Chemical Formula 4 is a compound represented by Chemical Formula 4a below.

11 . (canceled)

12 . (canceled)

13 . (canceled)

Assignees

• Lg Chemical Ltd

Inventors

• Lee Sang-Mi
• Lee Ro-Mi
• Kim No-Ma

Classifications

• C08F8/42 Primary

  Introducing metal atoms or metal-containing groups · CPC title

• C07D207/06

  with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms · CPC title

• B60C1/0016 Primary

  Compositions of the tread · CPC title

• C08K3/00

  Use of inorganic substances as compounding ingredients · CPC title

• C08C19/44

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