Catalyst composition for preparing conjugated diene-based polymer and conjugated diene-based polymer prepared using the same

Patent metadata

Field	Value
Publication number	US-10995165-B2
Application number	US-201916454888-A
Country	US
Kind code	B2
Filing date	Jun 27, 2019
Priority date	Jun 24, 2015
Publication date	May 4, 2021
Grant date	May 4, 2021

Abstract

The present invention provides a catalyst composition including a functionalizing agent of the following Formula 1 together with a rare earth metal compound, an alkylating agent, and a halogen compound, having good catalytic activity and polymerization reactivity and useful for the preparation of a conjugated diene-based polymer having high linearity and excellent processability, and a conjugated diene-based polymer prepared using the catalyst composition

(X 1 ) a —Sn—(X 2 ) 4-a   [Formula 1]

wherein, a, X 1 , and X 2 are the same as defined in the disclosure.

First claim

The invention claimed is:

1. A conjugated diene-based polymer comprising:
a functional group derived from a functionalizing agent of the following Formula 1:
(X 1 ) a —Sn—(X 2 ) 4-a   [Formula 1]

in Formula 1,
a is an integer of 1 to 3,
X 1 and X 2 are each independently selected from the group consisting of a hydrogen atom, monovalent C 1-20 hydrocarbon, —OR a , —NR b R c , —SiR d R e R f , and a covalent bonding functional group, where at least one of X 1 and X 2 includes the covalent bonding functional group, where R a , R b , R c , R d , R e and R f are each independently selected from the group consisting of a hydrogen atom, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 aralkyl, —NR′R″, and a covalent bonding functional group, where R′ and R″ are each independently selected from the group consisting of a hydrogen atom, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 aralkyl, and a covalent bonding functional group, and
the covalent bonding functional group is a functional group containing a carbon-carbon double bond.

2. The conjugated diene-based polymer of claim 1 , wherein the functionalizing agent comprises one of the following Formulae 2a to 2n, or a mixture of at least two thereof:

in Formulae 2a to 2n, Me means methyl, nBu means n-butyl, Ph means phenyl, TMS means trimethylsilyl, and Oft means ethoxy.

3. The conjugated diene-based polymer of claim 1 , wherein the polymer has a Mooney viscosity of 10 MU to 90 MU at 100° C. and a polydispersity of 3.4 or less.

4. A method for preparing the conjugated diene-based polymer of claim 1 , the method comprising:
polymerizing conjugated diene-based monomers in the presence of a catalyst composition, wherein the catalyst composition comprises
a functionalizing agent of the following Formula 1;
a rare earth metal compound;
an alkylating agent; and
a halogen compound:
(X 1 ) a —Sn—(X 2 ) 4-a   [Formula 1]

in Formula 1,
a is an integer of 1 to 3,
X 1 and X 2 are each independently selected from the group consisting of a hydrogen atom, monovalent C 1-20 hydrocarbon, —OR a , —NR b R c , —SiR d R e R f , and a covalent bonding functional group, where at least one of X 1 and X 2 includes the covalent bonding functional group, where R a , R b , R c , R d , R e and R f are each independently selected from the group consisting of a hydrogen atom, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 aralkyl, —SiR′R″R′″, and a covalent bonding functional group, where R′, R″ and R′″ are each independently selected from the group consisting of a hydrogen atom, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 aralkyl, and a covalent bonding functional group, and
the covalent bonding functional group is a functional group containing a carbon-carbon double bond.

5. The method of claim 4 , wherein the rare earth metal compound comprises a neodymium compound of the following Formula 3:

in Formula 3, R 1 to R 3 are each independently a hydrogen atom, or linear or branched C 1-12 alkyl.

6. The method of claim 5 , wherein the neodymium compound is Formula 3, in which R 1 is linear or branched C 6-8 alkyl, and R 2 and R 3 are each independently linear or branched C 2-6 alkyl.

7. The method of claim 5 , wherein the neodymium compound comprises 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(2,2-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 , Nd(2-ethyl-2-hexyl nonanoate) 3 , or a mixture of at least two thereof.

8. The method of claim 4 , wherein the alkylating agent comprises an organoaluminum compound of the following Formula 4:
Al(R) z (X) 3-z   [Formula 4]

in Formula 4,
R is each independently a hydrocarbyl group; or a heterohydrocarbyl group comprising at least one heteroatom of a nitrogen atom, an oxygen atom, a boron atom, a silicon atom, a sulfur atom or a phosphor atom in a hydrocarbyl structure,
X is each independently selected from the group consisting of a hydrogen atom, a halogen atom, a carboxyl group, an alkoxy group, and an aryloxy group, and
Z is an integer of 1 to 3.

9. A rubber composition comprising the conjugated diene-based polymer of claim 1 .

10. A tire part comprising the rubber composition of claim 9 .

Assignees

• Lg Chemical Ltd

Inventors

• Kang Suk Youn
• Choi Soo Young
• Cho Woo Jin
• Yoo Suk Joon
• Ahn Jeong Heon
• Ryu Jin Sook

Classifications

• C08F136/06 Primary

  Butadiene · CPC title

• B60C1/00 Primary

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

• C08L9/00

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

• C08G2380/00

  Tyres · CPC title

• C08F210/12

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