Conjugated diene-based polymer

Patent metadata

Field	Value
Publication number	US-10040876-B2
Application number	US-201515503900-A
Country	US
Kind code	B2
Filing date	Nov 18, 2015
Priority date	Nov 20, 2014
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

The present invention provides 1,4-cis polybutadiene having high linearity with an −S/R value of 1 or greater at 100° C., and accordingly, is capable of reducing resistance properties, particularly rolling resistance, and greatly enhancing fuel efficiency properties when used in a rubber composition.

First claim

What is claimed is:

1. 1,4-cis polybutadiene, which has a −S/R (stress/relaxation) value of 1 or greater at 100° C.,
wherein the conjugated diene-based polymer has a weight average molecular weight (Mw) of 740,000 g/mol to 2,500,000 g/mol, and a number average molecular weight (Mn) of 310,000 g/mol to 1,000,000 g/mol,
which is obtained by preparing a mixture of a molecular weight modifier and, as a monomer, 1,3-butadiene or a butadiene derivative prior to polymerization;
and polymerization reacting the mixture using a catalyst composition,
wherein the catalyst composition includes a lanthanide rare earth element-containing compound.

2. The 1,4-cis polybutadiene of claim 1 , which has a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 3 or less.

3. The 1,4-cis polybutadiene of claim 1 , which has Mooney viscosity of 30 to 90 at 100° C.

4. The 1,4-cis polybutadiene of claim 1 , which has 95% or higher cis-1,4 bond content.

5. The 1,4-cis polybutadiene of claim 1 , wherein the catalyst composition further includes a modified methylaluminoxane, a halogen compound and an aliphatic hydrocarbon-based solvent.

6. The 1,4-cis polybutadiene of claim 1 , wherein the molecular weight modifier includes any one or a mixture of two or more selected from the group consisting of trihydrocarbylaluminum, dihydrocarbylaluminum hydride, hydrogen and silane compounds.

7. The 1,4-cis polybutadiene of claim 1 , wherein the molecular weight modifier is used in a molar ratio of 1 to 100 with respect to 1 mol of the lanthanide rare earth element-containing compound.

8. The 1,4-cis polybutadiene of claim 5 , wherein the catalyst composition is a pre-mixture of the lanthanide rare earth element-containing compound, the modified methylaluminoxane, the halogen compound and the aliphatic hydrocarbon-based solvent.

9. The 1,4-cis polybutadiene of claim 5 , wherein the catalyst composition includes the lanthanide rare earth element-containing compound in an amount of 0.01 mmol to 0.25 mmol with respect to 100 g of the monomer.

10. The 1,4-cis polybutadiene of claim 5 , wherein the catalyst composition includes the lanthanide rare earth element-containing compound in 0.01 mmol to 0.25 mmol, the modified methylaluminoxane in 0.05 mmol to 50.0 mmol, the halogen compound in 0.01 mmol to 2.5 mmol and the aliphatic hydrocarbon-based solvent in 5 mmol to 200 mmol with respect to 100 g of the monomer.

11. The 1,4-cis polybutadiene of claim 5 , wherein the catalyst composition includes the lanthanide rare earth element-containing compound and the modified methylaluminoxane in a molar ratio of 1.0:5.0 to 1.0:200.

12. The 1,4-cis polybutadiene of claim 5 , wherein the catalyst composition includes the modified methylaluminoxane in 5 mols to 200 mols, the halogen compound in 1 mol to 10 mols and the aliphatic hydrocarbon-based solvent in 20 mols to 20,000 mols with respect to 1 mol of the lanthanide rare earth element-containing compound.

13. The 1,4-cis polybutadiene of claim 1 , wherein the lanthanide rare earth element-containing compound includes a neodymium compound of the following Chemical Formula 1:

wherein, in Chemical Formula 1, R1 to R3 are each independently a hydrogen atom, or a linear or branched alkyl group having 1 to 12 carbon atoms.

14. The 1,4-cis polybutadiene of claim 13 , wherein the lanthanide rare earth element-containing compound includes a neodymium compound in which, in Chemical Formula 1, R1 is a linear or branched alkyl group having 6 to 12 carbon atoms, and R2 and R3 are each independently a hydrogen atom or a linear or branched alkyl group having 2 to 8 carbon atoms, but R2 and R3 are not both hydrogen atoms at the same time.

15. The 1,4-cis polybutadiene of claim 1 , wherein the lanthanide rare earth element-containing compound includes any one or a mixture of two or more selected from the group consisting of Nd(2,2-diethyl decanoate)3, Nd(2,2-dipropyl decanoate)3, Nd(2,2-dibutyl decanoate)3, Nd(2,2-dihexyl decanoate)3, Nd(2,2-dioctyl decanoate)3, Nd(2-ethyl-2-propyl decanoate)3, Nd(2-ethyl-2-butyl decanoate)3, Nd(2-ethyl-2-hexyl decanoate)3, Nd(2-propyl-2-butyl decanoate)3, Nd(2-propyl-2-hexyl decanoate)3, Nd(2-propyl-2-isopropyl decanoate)3, Nd(2-butyl-2-hexyl decanoate)3, Nd(2-hexyl-2-octyl decanoate)3, Nd(2-t-butyl decanoate)3, Nd(2,2-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate)3, Nd(2,2-dipropyl nonanoate)3, Nd(2,2-dibutyl nonanoate)3, Nd(2,2-dihexyl nonanoate)3, Nd(2-ethyl-2-propyl nonanoate)3 and Nd(2-ethyl-2-hexyl nonanoate)3.

16. The 1,4-cis polybutadiene of claim 5 , wherein, in the modified methylaluminoxane, 50 mol % to 90 mol % of a methyl group of the methylaluminoxane is substituted with a hydrocarbon group having 2 to 20 carbon atoms.

17. The 1,4-cis polybutadiene of claim 5 , wherein the aliphatic hydrocarbon-based solvent includes any one or a mixture of two or more selected from the group consisting of linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms.

18. The 1,4-cis polybutadiene of claim 5 , wherein the halogen compound includes any one or a mixture of two or more selected from the group consisting of elemental halogen compounds, interhalogen compounds, halogenated hydrogen, organic halides, non-metal halides, metal halides and organic metal halides.

19. The 1,4-cis polybutadiene of claim 5 , wherein the catalyst composition does not include diisobutylaluminum hydride.

Assignees

• Lg Chemical Ltd

Inventors

• Oh Kyoung Hwan
• Kim Won Hee
• Bae Hyo Jin
• Ahn Jeong Heon
• Cho Woo Jin
• Kang Suk Youn

Classifications

• C08L9/00

  Compositions of homopolymers or copolymers of conjugated diene hydrocarbons · CPC title

• C08K3/04

  Carbon · CPC title

• C08F4/619

  Component covered by group C08F4/60 containing a transition metal-carbon bond {(C08F4/60003 - C08F4/60196 take precedence)} · CPC title

• B60C1/00

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

• C08F4/622

  Component covered by group C08F4/62 with an organo-aluminium compound {(C08F4/62003 - C08F4/62196 take precedence)} · CPC title