Modified conjugated diene-based polymer, method for preparing the same and rubber composition including the same

Patent metadata

Field	Value
Publication number	US-10414841-B2
Application number	US-201615546119-A
Country	US
Kind code	B2
Filing date	Oct 7, 2016
Priority date	Oct 8, 2015
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

The present disclosure relates to a modified conjugated diene-based polymer having excellent affinity with a filler, a method for preparing the same, a rubber composition including the same and a tire manufactured using the rubber composition. The modified conjugated diene-based polymer according thereto has a tin-based compound-derived group bind on one end, and a silane-based compound-derived group bind on the other end, and therefore, may have excellent affinity with a carbon black-based filler as well as a silica-based filler. Accordingly, a rubber composition including the modified conjugated diene-based polymer may have excellent processability, and as a result, processed goods (for example, tires) manufactured using the rubber composition may have excellent tensile strength, wear resistance and viscoelastic property.

First claim

What is claimed is:

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

wherein, in Chemical Formula 1,
R, R 4 and R 5 are each independently a hydrocarbon group having 1 to 20 carbon atoms;
R 2 and R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen;
R 2 and R 3 are linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
P is a modified conjugated diene-based polymer chain;
X is a halogen group;
A is a tertiary amine;
a and b are each independently an integer of 1 to 4; and
a+b≤4.

2. The modified conjugated diene-based polymer of claim 1 , wherein, in Chemical Formula 1, R, R 4 and R 5 are each independently an alkyl group having 1 to 10 carbon atoms, and R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms; an alkyl group having 1 to 10 carbon atoms containing oxygen; or an alkyl group having 1 to 10 carbon atoms containing nitrogen.

3. The modified conjugated diene-based polymer of claim 1 , wherein, in Chemical Formula 1, R, R 4 and R 5 are each independently an alkyl group having 1 to 6 carbon atoms, and R 2 and R 3 are each independently an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms containing oxygen.

4. The modified conjugated diene-based polymer of claim 1 , wherein, in Chemical Formula 1, X is selected from among F, Cl, Br and I.

5. The modified conjugated diene-based polymer of claim 1 , wherein the polymer contains 80 ppm to 700 ppm of silica (Si).

6. The modified conjugated diene-based polymer of claim 1 , wherein the polymer contains 50 ppm to 550 ppm of tin (Sn).

7. The modified conjugated diene-based polymer of claim 1 , which is a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer.

8. The modified conjugated diene-based polymer of claim 1 , wherein the copolymer includes the aromatic vinyl-based monomer-derived unit is 40% by weight or less.

9. The modified conjugated diene-based polymer of claim 1 , wherein the polymer has a weight average molecular weight of 250,000 g/mol to 1,600,000 g/mol.

10. The modified conjugated diene-based polymer of claim 1 , wherein a ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn) (Mw/Mn) of the polymer is from 1.7 to 3.5.

11. A method for preparing the modified conjugated diene-based polymer of claim 1 represented by the following Chemical Formula 1, the method comprising:
1) preparing an active polymer having alkali metals bind on both ends by polymerizing a conjugated diene-based monomer, or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent under the presence of a multifunctional anion polymerization initiator;
2) reacting the polymer with a tin-based compound represented by the following Chemical Formula 2; and
3) after the reaction, reacting the product of the active polymer and the tin-based compound with an aminosilane-based compound represented by the following Chemical Formula 3:

wherein, in Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3,
R, R 4 and R 5 are each independently a hydrocarbon group having 1 to 20 carbon atoms;
R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms; or a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen;
R 2 and R 3 are linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
P is a modified conjugated diene-based polymer chain;
X is a halogen group;
A is a tertiary amine;
a, b and m are each independently an integer of 1 to 4;
and
a+b≤4.

12. The method for preparing the modified conjugated diene-based polymer of claim 11 , wherein the multifunctional anion polymerization initiator is prepared by reacting an aromatic compound and an organolithium compound in a hydrocarbon solvent.

13. The method for preparing the modified conjugated diene-based polymer of claim 12 , wherein the aromatic compound and the organolithium compound are reacted in a molar ratio of 1:1 to 2.

14. The method for preparing the modified conjugated diene-based polymer of claim 12 , wherein the aromatic compound is one or more types selected from the group consisting of o-diisopropenylbenzene, m-diisopropenylbenzene, p-diisopropenylbenzene, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, 1,2,4-trivinylbenzene, 1,2-vinyl-3,4-dimethylbenzene, 1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4′-trivinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene and 1,5,6-trivinyl-3,7-diethylnaphthalene.

15. The method for preparing the modified conjugated diene-based polymer of claim 12 , wherein the organolithium compound is one or more types selected from the group consisting of ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, phenyllithium, lithium acetylamide and lithium isopropylamide.

16. The method for preparing the modified conjugated diene-based polymer of claim 11 , wherein the multifunctional anion polymerization initiator is used in 0.10 parts by weight to 0.5 parts by weight based on a total of 100 parts by weight of the monomer.

17. The method for preparing the modified conjugated diene-based polymer of claim 11 , wherein the tin-based compound represented by Chemical Formula 2 is one or more types selected from the group consisting of methyl trichlorotin, dimethyl dichlorotin, ethyl trichlorotin, diethyl dichlorotin, butyl trichlorotin, dibutyl dichlorotin, octyl trichlorotin, dioctyl dichlorotin, methyl tribromotin, dimethyl dibromotin, octyl tribromotin, dioctyl dibromotin, tetrachlorotin, tetrabromotin, tetraiodotin, cyclohexyl trichlorotin and phenyl trichlorotin.

18. The method for preparing the modified conjugated diene-based polymer of claim 11 , wherein the aminosilane-based compound represented by Chemical Formula 3 is 3-(diethoxy(methyl)silyl)-N,N-diethylpropane-1-amine or 2-(N,N-dimethylaminopropyl)2,5,5-trimethyl-1,3,2-dioxysilane.

19. The method for preparing the modified conjugated diene-based polymer of claim 11 , wherein the tin-based compound represented by Chemical Formula 2 is used such that tin in the tin-based compound is in 0.05 mol to 0.25 mol per 1 mol of lithium in the multifunctional anion polymerization initiator.

20. The method for preparing the modified conjugated diene-based polymer of claim 11 , wherein the aminosilane-based compound represented by Chemical Formula 3 is used such that silica in the aminosilane-based compound is in 0.1 mol to 1.0 mol per 1 mol of lithium in the multifunctional anion polymerization initiator.

Assignees

• Lg Chemical Ltd

Inventors

• Chun Moon Seok
• Lee Soo Yong
• Lee Seong Du
• Kim No Ma
• Kwon Kyung An

Classifications

• C08F236/06

  Butadiene · CPC title

• C08F236/04 Primary

  conjugated · CPC title

• C08F36/14

  containing elements other than carbon and hydrogen · CPC title

• C08K3/04

  Carbon · CPC title

• C08G79/12 Primary

  a linkage containing tin · CPC title