End-functional conjugated diene-based polymer and manufacturing method therefor

Patent metadata

Field	Value
Publication number	US-10030079-B2
Application number	US-201414911993-A
Country	US
Kind code	B2
Filing date	Aug 26, 2014
Priority date	Oct 17, 2013
Publication date	Jul 24, 2018
Grant date	Jul 24, 2018

Abstract

Disclosed are an end-functionalized conjugated diene-based polymer represented by Chemical Formula 1 and a method of preparing the same.

First claim

The invention claimed is:

1. An end-functionalized conjugated diene-based polymer represented by Chemical Formula 1 below,

wherein in Chemical Formula 1, R 1 is an alkyl group or an alkylsilyl group, R 2 is an alkylene group, R 3 and R 4 are an alkyl group, a is an integer of 1 to 3, l and k are an integer of 0 to 2, m is an integer of 1 to 3, with l+k+m satisfying 3, P is a conjugated diene-based polymer chain, A is a compound represented by Chemical Formula 2 below, and b is an integer of 1 to 3, and when k is 2, two R 1 s linked to nitrogen are identical to or different from each other, and in a same manner, when l and m are 2 or more, corresponding groups are identical to or different from each other,

wherein in Chemical Formula 2, n is 1 or 2, R 1 is hydrogen or a C1˜5 alkyl group, R 2 is C1˜5 alkylene group, and D is a group containing oxygen or amine.

2. The end-functionalized conjugated diene-based polymer of claim 1 , wherein the compound represented by Chemical Formula 2 comprises any one or more selected from the group consisting of 3-(2-pyrrolidinoethyl)styrene, 4-(2-pyrrolidinoethyl)styrene, and 3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene.

3. The end-functionalized conjugated diene-based polymer of claim 1 , wherein l is 0 or 1.

4. The end-functionalized conjugated diene-based polymer of claim 1 , wherein k is 0 or 1.

5. The end-functionalized conjugated diene-based polymer of claim 1 , wherein in Chemical Formula 1, k is 1, l is 1, and m is 1.

6. The end-functionalized conjugated diene-based polymer of claim 1 , wherein the conjugated diene-based polymer chain is a random copolymer chain comprising a conjugated diene-based monomer and a vinyl aromatic monomer.

7. The end-functionalized conjugated diene-based polymer of claim 1 , wherein the end-functionalized conjugated diene-based polymer has a number average molecular weight of 1,000˜2,000,000 g/mol.

8. The end-functionalized conjugated diene-based polymer of claim 1 , wherein the end-functionalized conjugated diene-based polymer has a vinyl content of 18% or more.

9. The end-functionalized conjugated diene-based polymer of claim 1 , wherein the end-functionalized conjugated diene-based polymer contains 10˜40 wt % of an aromatic vinyl monomer based on 100 wt % in total of a conjugated diene-based monomer and an aromatic vinyl monomer.

10. The end-functionalized conjugated diene-based polymer of claim 1 , wherein the end-functionalized conjugated diene-based polymer has a Mooney viscosity of 65 or more.

11. A method of preparing an end-functionalized conjugated diene-based polymer, comprising:
(a) polymerizing a conjugated diene-based monomer or a conjugated diene-based 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 alkali metal end with a compound represented by Chemical Formula 2 below; and
(c) modifying the active polymer with a compound represented by Chemical Formula 3 below,

wherein in Chemical Formula 2, n is 1 or 2, R 1 is hydrogen or a C1˜5 alkyl group, R 2 is a C1˜5 alkylene group, and D is a group containing oxygen or amine,

wherein in Chemical Formula 3, R 1 is an alkyl group or an alkylsilyl group, R 2 is an alkylene group, R 3 and R 4 are an alkyl group, a is an integer of 1 to 3, and n is an integer of 0 to 2, and when n is 2, two R 1 s linked to nitrogen are identical to or different from each other, and in a same manner, when 3−n is 2 or more, corresponding groups are identical to or different from each other.

12. The method of claim 11 , wherein the compound represented by Chemical Formula 2 comprises any one or more selected from the group consisting of 3-(2-pyrrolidinoethyl)styrene, 4-(2-pyrrolidinoethyl)styrene, and 3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene.

13. The method of claim 11 , wherein the compound represented by Chemical Formula 2 is contained in an amount of 0.05˜10 wt % based on a total monomer amount.

14. The method of claim 11 , wherein the organometallic compound is an organo-alkali metal compound.

15. The method of claim 11 , wherein the organometallic compound is used in an amount of 0.01˜10 mmol based on 100 g in total of the monomer.

16. The method of claim 11 , wherein a molar ratio of the organometallic compound to the compound represented by Chemical Formula 3 is 1:0.1˜1:10.

17. The method of claim 11 , wherein polymerizing in (a) is performed with additional use of a polar additive.

18. The method of claim 17 , wherein the polar additive is used at a molar ratio of 0.1˜10 relative to 1 mmol of the organometallic compound.

19. An end-functionalized conjugated diene-based polymer rubber composition, comprising 100 parts by weight of the end-functionalized conjugated diene-based polymer of claim 1 , and 0.1˜200 parts by weight of an inorganic filler.

20. The end-functionalized conjugated diene-based polymer rubber composition of claim 19 , comprising 100 parts by weight of a polymer mixture comprising 10˜100 wt % of the end-functionalized conjugated diene-based polymer and 0˜90 wt % of another end-functionalized conjugated diene-based polymer, 0˜100 parts by weight of carbon black, 5˜200 parts by weight of silica, and 2˜20 parts by weight of a silane coupling agent.

21. The end-functionalized conjugated diene-based polymer rubber composition of claim 19 , wherein the inorganic filler is a silica-based filler.

22. A tire comprising the end-functionalized conjugated diene-based polymer rubber composition of claim 19 .

Assignees

• Lg Chemical Ltd

Inventors

• Lee Romi
• Kim Yujin
• Kim Noma

Classifications

• C08L15/00

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

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08K3/36

  Silica · CPC title

• B60C1/00 Primary

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

• C08F8/30

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title