End-functionalized conjugated diene-based polymer and process for producing same

Patent metadata

Field	Value
Publication number	US-2016208024-A1
Application number	US-201414914339-A
Country	US
Kind code	A1
Filing date	Oct 16, 2014
Priority date	Oct 17, 2013
Publication date	Jul 21, 2016
Grant date	—

Abstract

Disclosed are a modified conjugated diene-based polymer represented by Chemical Formula 1, a method of preparing the same, and a rubber composition including the same.

First claim

1 . A modified conjugated diene-based polymer represented by Chemical Formula 1 below:

in Chemical Formula 1, R 1 , R 2 , and R 5 are each independently a C1-C10 alkylene group, R 3 , R 4 , R 6 and R 7 are each independently a C1-C10 alkyl group, R 8 is hydrogen or a C1-C10 alkyl group, P is a conjugated diene-based polymer chain, B is Chemical Formula 13 below, a and c are each independently 0, 1, or 2, b and d are each independently 1, 2, or 3, a+b and c+d are each independently 1, 2, or 3, and A is

wherein R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or a C1-C10 alkyl group.

(in Chemical Formula 13, n is 1 or 2, R 1 is hydrogen or a C1-C5 alkyl group, R 2 is a bond or a C1-C5 alkylene group, and D is a group containing oxygen or NR 3 R 4 , wherein R 3 and R 4 are each independently hydrogen or a C1-C5 alkyl group, and R 3 and R 4 are linked to form a heterocycle containing N.)

2 . The modified conjugated diene-based polymer of claim 1 , wherein Chemical Formula 1 is represented by Chemical Formula 2 or Chemical Formula 3 below:

in Chemical Formulas 2 and 3, R 15 , R 16 , R 18 , R 19 , R 22 , R 23 , R 25 , and R 26 are each independently a C1-C5 alkyl group, R 13 , R 14 , R 17 , R 20 , R 21 , and R 24 are each independently a C1-C5 alkylene group, P is a conjugated diene-based polymer chain, B is Chemical Formula 13 below, a and c are each independently 0, 1, or 2, b and d are each independently 1, 2, or 3, and a+b and c+d are each independently 1, 2, or 3.

(in Chemical Formula 13, n is 1 or 2, R 1 is hydrogen or a C1-C5 alkyl group, R 2 is a bond or a C1-C5 alkylene group, and D is a group containing oxygen or NR 3 R 4 , wherein R 3 and R 4 are each independently hydrogen or a C1-C5 alkyl group, and R 3 and R 4 are linked to form a heterocycle containing N.)

3 . The modified conjugated diene-based polymer of claim 1 , wherein Chemical Formula 1 is represented by Chemical Formula 4 or Chemical Formula 5 below:

in Chemical Formulas 4 and 5, P is a conjugated diene-based polymer chain, B is Chemical Formula 13 below, a and c are each independently 0, 1, or 2, b and d are each independently 1, 2, or 3, and a+b and c+d are each independently 1, 2, or 3.

(in Chemical Formula 13, n is 1 or 2, R 1 is hydrogen or a C1-C5 alkyl group, R 2 is a bond or a C1-C5 alkylene group, and D is a group containing oxygen or NR 3 R 4 , wherein R 3 and R 4 are each independently hydrogen or a C1-C5 alkyl group, and R 3 and R 4 are linked to form a heterocycle containing N.)

4 . The modified conjugated diene-based polymer of claim 1 , wherein Chemical Formula 1 is represented by Chemical Formula 6 or Chemical Formula 7 below.

5 . The modified conjugated diene-based polymer of claim 1 , wherein Chemical Formula 13 comprises any one or more selected from the group consisting of 4,4′-vinylidenebis(n,n-dimethylaniline), 3-(2-pyrrolidino ethyl)styrene, 4-(2-pyrrolidino ethyl) styrene, and (3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene.

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

7 . The modified conjugated diene-based polymer of claim 1 , wherein the modified conjugated diene-based polymer has a polydispersity index (Mw/Mn) of 0.5 to 10.

8 . The modified conjugated diene-based polymer of claim 1 , wherein the modified conjugated diene-based polymer has a vinyl content of 10 wt % or more.

9 . The modified conjugated diene-based polymer of claim 1 , wherein the conjugated diene-based polymer chain is derived from a homopolymer of a conjugated diene monomer or a copolymer of a conjugated diene monomer and a vinyl aromatic monomer.

10 . The modified conjugated diene-based polymer of claim 1 , wherein the modified conjugated diene-based polymer includes 0.0001 to 50 parts by weight of an aromatic vinyl monomer based on 100 parts by weight in total of a conjugated diene monomer and the aromatic vinyl monomer.

11 . The modified conjugated diene-based polymer of claim 1 , wherein the modified conjugated diene-based polymer has a Mooney viscosity of 40 or more.

12 . A method of preparing a modified conjugated diene-based polymer, comprising:
(a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and a vinyl aromatic monomer with an organometallic compound using a solvent, thus forming an active polymer having a metal end; (b) end-capping the active polymer having an alkali metal end with a compound represented by Chemical Formula 13 below; and (c) modifying the active polymer with a compound represented by Chemical Formula 8 below:

in Chemical Formula 8, R 1 , R 2 , and R 5 are each independently a C1-C10 alkylene group, R 3 , R 4 , R 6 and R 7 are each independently a C1-C10 alkyl group, R 8 is hydrogen or a C1-C10 alkyl group, a and c are each independently 0, 1, or 2, and A is

wherein R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or a C1-C10 alkyl group.

13 . The method of claim 12 , wherein Chemical Formula 8 is represented by Chemical Formula 9 or Chemical Formula 10 below:

in Chemical Formulas 9 and 10, a and c are each independently 0, 1, or 2.

14 . The method of claim 12 , wherein Chemical Formula 8 is represented by Chemical Formula 11 or 12 below.

15 . The method of claim 12 , wherein Chemical Formula 13 comprises any one or more selected from the group consisting of 4,4′-vinylidenebis(n,n-dimethylaniline), 3-(2-pyrrolidino ethyl)styrene, 4-(2-pyrrolidino ethyl)styrene, and 3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene.

16 . The method of claim 12 , wherein the organometallic compound is used in an amount of 0.01 to 10 mmol based on 100 g in total of the monomer.

17 . The method of claim 12 , wherein a molar ratio of the organometallic compound and the compound represented by Chemical Formula 8 is 1:0.1 to 1:10.

18 . The method of claim 12 , wherein the polymerizing in (a) is performed with additional use of a polar additive.

19 . The method of claim 18 , wherein the polar additive is added in an amount of 0.001 to 10 g based on 1 mmol in total of the organometallic compound.

20 . (canceled)

Assignees

• Lg Chemical Ltd

Inventors

• Kim Yujin
• Lee Romi
• Kim Noma

Classifications

• C08K3/36

  Silica · CPC title

• C08F8/42 Primary

  Introducing metal atoms or metal-containing groups · CPC title

• B60C1/00

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title

• C08C19/22

  Incorporating nitrogen atoms into the molecule · CPC title

• C08L15/00

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