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

Patent metadata

Field	Value
Publication number	US-10676543-B2
Application number	US-201715766480-A
Country	US
Kind code	B2
Filing date	Jul 5, 2017
Priority date	Aug 12, 2016
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

The present invention relates to a modified conjugated diene-based polymer, a method of preparing the same, and a rubber composition including the same, and more specifically provides a rubber composition which includes a repeating unit derived from a conjugated diene-based monomer having a trans-1,4 bond content of 80 wt % or more and a functional group derived from an alkoxysilane-based modifier, a method of preparing the same, and a rubber composition including the same.

First claim

The invention claimed is:

1. A modified conjugated diene-based polymer, comprising a repeating unit derived from a conjugated diene-based monomer having a trans-1,4 bond content of 80 wt % or more, and a functional group derived from an alkoxysilane-based modifier,
wherein the modified conjugated diene-based polymer includes a repeating unit derived from an aromatic vinyl monomer,
wherein the alkoxysilane-based modifier is one or more selected from the group consisting of alkoxysilane-based modifiers represented by the following Formulas 1b to 1r, and 1t to 1y:

in Formulas 1b to 1r, and 1t to 1y, Me is a methyl group, and Et is an ethyl group.

2. The modified conjugated diene-based polymer according to claim 1 , wherein the modified conjugated diene-based polymer is a random copolymer including the repeating unit derived from a conjugated diene-based monomer at 50 to 95 wt % and the repeating unit derived from an aromatic vinyl monomer at 5 to 50 wt %.

3. The modified conjugated diene-based polymer according to claim 1 , wherein the modified conjugated diene-based polymer is a terminal modified conjugated diene-based polymer.

4. The modified conjugated diene-based polymer according to claim 1 , wherein the modified conjugated diene-based polymer has a number average molecular weight (Mn) in a range of 10,000 to 500,000 g/mol and a molecular weight distribution (Mw/Mn) in a range of 1.1 to 3.

5. A method of preparing a modified conjugated diene-based polymer, comprising:
i) polymerizing a conjugated diene-based monomer and an aromatic vinyl monomer in the presence of a catalyst composition including an organic alkaline earth metal compound and an organic alkali metal compound to prepare an active polymer including an alkali metal terminal and a repeating unit derived from a conjugated diene-based monomer with a trans-1,4 bond content of 80 wt % or more; and
ii) modifying the active polymer by an alkoxysilane-based modifier,
wherein the alkoxysilane-based modifier is one or more selected from the group consisting of alkoxysilane-based modifiers represented by the following Formulas 1b to 1r, and 1t to 1y:

in Formulas 1b to 1r, and 1t to 1y, Me is a methyl group, and Et is an ethyl group.

6. The method according to claim 5 , wherein a modification ratio of the modified conjugated diene-based polymer is 50% or more.

7. The method of claim 5 , wherein the organic alkaline earth metal compound is one or more selected from the group consisting of a barium salt of an aliphatic alcohol having 1 to 30 carbon atoms or an aromatic alcohol having 5 to 30 carbon atoms; a strontium salt of an aliphatic alcohol having 1 to 30 carbon atoms or an aromatic alcohol having 5 to 30 carbon atoms; and a calcium salt of an aliphatic alcohol having 1 to 30 carbon atoms or an aromatic alcohol having 5 to 30 carbon atoms.

8. The method of claim 7 , wherein the organic alkaline earth metal compound is one or more selected from the group consisting of barium di(ethylene glycol) ethyl ether, barium di(ethylene glycol) propyl ether, barium di(N,N-dimethylethylene glycol) ethyl ether, barium di(ethylene glycol) hexyl ether, barium mentholate and barium thymolate.

9. The method of claim 5 , wherein the organic alkali metal compound is one or more selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyllithium, hexyllithium, n-decyllithium, t-oxyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

10. The method of claim 5 , wherein the catalyst composition includes an organoaluminum compound represented by the following Formula 2:

in Formula 2, R 1 to R 3 each independently represent hydrogen, a linear or branched 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 alkylaryl group having 6 to 30 carbon atoms, an arylalkyl group having 6 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms.

11. The method of claim 10 , wherein the organoaluminum compound is one or more selected from the group consisting of diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl n-propyl aluminum hydride, p-tolyloisopropyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, diethyl aluminum ethoxide, diisobutyl aluminum ethoxide, dipropyl aluminum methoxide, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyl diphenyl aluminum, ethyl di-p-tolyl aluminum, ethyl dibenzyl aluminum, diethylphenyl aluminum, diethyl p-tolyl aluminum and diethyl benzyl aluminum.

12. The method of claim 5 , wherein the polymerization of Step i) is performed by including a polar additive.

13. The method of claim 12 , wherein the polar additive is one or more selected from the group consisting of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamylether, dipropyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.

Assignees

• Lg Chemical Ltd

Inventors

• Seo Kyung Chang
• Kim No Ma
• Lee Sang Mi
• Kim Yu Jin

Classifications

• C08K5/0025

  Crosslinking or vulcanising agents; including accelerators · CPC title

• C08L91/00

  Compositions of oils, fats or waxes; Compositions of derivatives thereof · CPC title

• C08K5/54

  Silicon-containing compounds {(C08K5/0091 takes precedence)} · CPC title

• C08K2003/2296

  of zinc · CPC title

• C08F236/06

  Butadiene · CPC title