Modified conjugated diene-based polymer, modified rubber composition containing same, and method for preparing modified conjugated diene-based polymer

Patent metadata

Field	Value
Publication number	US-9834619-B2
Application number	US-201515117653-A
Country	US
Kind code	B2
Filing date	Jun 10, 2015
Priority date	Jun 16, 2014
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

Disclosed are a method of preparing a modified conjugated diene-based polymer, a modified conjugated diene-based polymer prepared thereby, a rubber composition including the modified conjugated diene-based polymer, and a tire including the rubber composition. The method of preparing the modified conjugated diene-based polymer includes (a) polymerizing a vinyl aromatic monomer and a conjugated diene monomer through continuous solution polymerization using a multifunctional anionic polymerization initiator in the presence of a hydrocarbon solvent, thus forming an active polymer having a reactive end; and (b) coupling or linking the reactive end of the active polymer with an alkylamino alkoxy silane compound.

First claim

The invention claimed is:

1. A method of preparing a modified conjugated diene-based polymer, comprising:
(a) polymerizing a conjugated diene monomer or a vinyl aromatic monomer and a conjugated diene monomer through continuous solution polymerization using a multifunctional anionic polymerization initiator in presence of a hydrocarbon solvent, thus forming an active polymer having a reactive end; and
(b) coupling or linking the reactive end of the active polymer with an aminoalkyl alkoxy silane compound,
wherein the multifunctional anionic polymerization initiator is an organo-alkali metal compound having two or more organometals,
the modified conjugated diene-based polymer has a single peak in a molecular weight range from 10,000 to 10,000,000 g/mol when analyzed using gel permeation chromatography (GPC), and a modification efficiency of 40% to 95%, and
the aminoalkyl alkoxy silane compound is any one of Chemical Formulas 1 to 3 below:
(R 1 —O) n R 2 3-n Si—R 3 -A  [Chemical Formula 1]

wherein, in Chemical Formula 1, R 1 is a C1-C20 hydrocarbon containing at least one oxygen or nitrogen, R 2 and R3 are C1-C20 hydrocarbons, A is amine, n is an integer of 1 to 3, two or three R 1 s are identical to or different from each other when n is 2 or 3, and two R 2 s are identical to or different from each other when n is 1;

wherein, in Chemical Formula 2, R 1 , R 2 and R 3 are C1-C20 hydrocarbons, and A is an amine;

wherein, in Chemical Formula 3, R 1 , R 2 and R 3 are C1-C20 hydrocarbons, and A is an amine.

2. The method of claim 1 , wherein the active polymer is a random copolymer comprising the conjugated diene monomer and the vinyl aromatic monomer.

3. The method of claim 2 , wherein the active polymer is a random copolymer resulting from anionic polymerization of the conjugated diene monomer and the vinyl aromatic monomer.

4. The method of claim 2 , wherein the random copolymer has a ratio of the conjugated diene monomer and the vinyl aromatic monomer ranging from 90:10 to 60:40.

5. The method of claim 1 , wherein the active polymer has a ratio of the conjugated diene monomer and the vinyl aromatic monomer ranging from 100:0 to 60:40.

6. The method of claim 1 , wherein the organo-alkali metal compound having two or more metals is a multi-lithium compound, and
wherein the organo group of the multi-lithium compound comprises at least one selected from 1,1-diphenylethylene (DPE) dimer, 1,3-divinylbenzene (DVB), 1,3-bis(1-phenylethenyl)benzene (PEB), 1,3-diisopropenylbenzene (DIB), 2,6-lutidine, or 1-bromo-4-(4′-bromophenoxy)-2-pentadecyl benzene.

7. The method of claim 1 , wherein the reactive end is a lithium metal end.

8. The method of claim 1 , wherein the modified conjugated diene-based polymer has a single peak molecular weight distribution of 1.5 or more, as measured using GPC.

9. A modified conjugated diene-based polymer, which is configured such that an end of a random copolymer comprising a conjugated diene monomer and a vinyl aromatic monomer is modified with an aminoalkyl alkoxy silane compound,
which has a modification efficiency of 40 to 95%,
wherein the modified conjugated diene-based polymer has a single peak in a molecular weight range from 10,000 to 10,000,000 g/mol when analyzed using GPC, and
the aminoalkyl alkoxy silane compound is any one of Chemical Formulas 1 to 3 below:
(R 1 —O) n R 2 3-n Si—R 3 -A  [Chemical Formula 1]

wherein, in Chemical Formula 1, R 1 is a C1-C20 hydrocarbon containing at least one oxygen or nitrogen, R 2 and R3 are C1-C20 hydrocarbons, A is amine, n is an integer of 1 to 3, two or three R 1 s are identical to or different from each other when n is 2 or 3, and two R 2 s are identical to or different from each other when n is 1;

wherein, in Chemical Formula 2, R 1 , R 2 and R 3 are C1-C20 hydrocarbons, and A is an amine;

wherein, in Chemical Formula 3, R 1 , R 2 and R 3 are C1-C20 hydrocarbons, and A is an amine.

10. The modified conjugated diene-based polymer of claim 9 ,
wherein the modified conjugated diene-based polymer has a single peak molecular weight distribution of 1.5 or more, as measured using GPC.

11. The modified conjugated diene-based polymer of claim 9 , wherein the random copolymer has a ratio of the conjugated diene monomer and the vinyl aromatic monomer ranging from 90:10 to 60:40.

12. A modified conjugated diene-based polymer, which is configured such that an end of an active polymer comprising a conjugated diene monomer is modified with an aminoalkyl alkoxy silane compound,
which has a modification efficiency of 40 to 95%,
wherein the modified conjugated diene-based polymer has a single peak in a molecular weight range from 10,000 to 10,000,000 g/mol when analyzed using GPC, and
the aminoalkyl alkoxy silane compound is any one of Chemical Formulas 1 to 3 below:
(R 1 —O) n R 2 3-n Si—R 3 -A  [Chemical Formula 1]

wherein, in Chemical Formula 1, R 1 is a C1-C20 hydrocarbon containing at least one oxygen or nitrogen, R 2 and R3 are C1-C20 hydrocarbons, A is amine, n is an integer of 1 to 3, two or three R 1 s are identical to or different from each other when n is 2 or 3, and two R 2 s are identical to or different from each other when n is 1;

wherein, in Chemical Formula 2, R 1 , R 2 and R 3 are C1-C20 hydrocarbons, and A is an amine;

wherein, in Chemical Formula 3, R 1 , R 2 and R 3 are C1-C20 hydrocarbons, and A is an amine.

13. The modified conjugated diene-based polymer of claim 12 ,
wherein the modified conjugated diene-based polymer has a single peak molecular weight distribution of 1.5 or more, as measured using GPC.

Assignees

• Lg Chemical Ltd

Inventors

• Chun Moon-Seok
• Lee Soo-Yong
• Lee Seong-Du

Classifications

• C08L9/10

  Latex (C08L9/04, C08L9/08 take precedence) · CPC title

• C08G77/42

  Block-or graft-polymers containing polysiloxane sequences (polymerising aliphatic unsaturated monomers on to a polysiloxane C08F283/12) · CPC title

• C08F2/04

  Polymerisation in solution (C08F2/32 takes precedence) · CPC title

• C08F230/08

  containing silicon · CPC title

• C08F210/12

  with conjugated diolefins, e.g. butyl rubber · CPC title