Method for preparing modified conjugated diene-based polymer

Patent metadata

Field	Value
Publication number	US-10920004-B2
Application number	US-201716342124-A
Country	US
Kind code	B2
Filing date	Dec 7, 2017
Priority date	Jan 3, 2017
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

Abstract

The present invention relates to a method for preparing a modified conjugated diene-based polymer, and more particularly, provides a method for preparing a modified conjugated diene-based polymer including a step of polymerizing a conjugated diene-based monomer in the presence of an organometal compound in a hydrocarbon solvent to prepare an active polymer which is coupled with an organometal (S1); and a step of reacting or coupling the active polymer prepared in step (S1) with a modifier (S2), wherein step (S1) is continuously performed in two or more polymerization reactors, and a polymerization conversion ratio in a first reactor among the polymerization reactors is 50% or less.

First claim

The invention claimed is:

1. A method for preparing a modified conjugated diene-based polymer comprising:
polymerizing a conjugated diene-based monomer in the presence of an organometal compound in a hydrocarbon solvent to prepare an active polymer which is coupled with an organometal (S1); and
a step of reacting or coupling the active polymer prepared in step (S1) with a modifier (S2),
wherein step (S1) is continuously performed in two or more polymerization reactors, and
a polymerization conversion ratio in a first polymerization reactor among the polymerization reactors is 50% or less.

2. The method according to claim 1 , wherein the polymerization step (S1) is performed at a temperature of 80° C. or less.

3. The method according to claim 1 , wherein the conjugated diene-based monomer and an aromatic vinyl monomer are copolymerized in the polymerization step (S1).

4. The method according to claim 1 , wherein a final polymerization conversion ratio of the polymerization step (S1) is 95% or more.

5. The method according to claim 1 , wherein a residence time of a polymer in the first polymerization reactor is from 1 minute to 40 minutes.

6. The method according to claim 1 , wherein a polar additive is included in the polymerization step (S1).

7. The method for preparing a modified conjugated diene-based polymer of claim 1 , wherein the modifier has an affinity with silica.

8. The method according to claim 1 , wherein the modifier is an alkoxysilane-based modifier.

9. The method according to claim 1 , wherein the modifier is injected into a modification reactor performing step (S2), or the modifier is injected into a transporting part transporting the active polymer prepared in the polymerization step (S1) to the modification reactor performing step (S2).

10. The method according to claim 1 , wherein the modifier is one or more selected from the group consisting of compounds represented by the following Formula 1 to Formula 6:
(R 4 —R 21 n N R 1 —Si(OR 2 ) a (R 3 ) 3-a ) m   [Formula 1]

in Formula 1,
R 1 is a single bond, or an alkylene group of 1 to 10 carbon atoms,
R 2 and R 3 are each independently an alkyl group of 1 to 10 carbon atoms,
R 4 is hydrogen, an alkyl group of 1 to 10 carbon atoms, a divalent, trivalent or tetravalent alkylsilyl group which is substituted with an alkyl group of 1 to 10 carbon atoms, or a heterocyclic group of 2 to 10 carbon atoms,
R 21 is a single bond, an alkylene group of 1 to 10 carbon atoms, or —[R 42 O] j —, where R 42 is an alkylene group of 1 to 10 carbon atoms, and
a and m are each independently an integer of 1 to 3, n is an integer of 0 to 3, and j is an integer of 1 to 30;

in Formula 2,
R 5 , R 6 and R 9 are each independently an alkylene group of 1 to 10 carbon atoms,
R 7 , R 8 , R 10 and R 11 are each independently an alkyl group of 1 to 10 carbon atoms,
R 12 is hydrogen or an alkyl group of 1 to 10 carbon atoms,
b and c are each independently an integer of 0 to 3, where b+c≥1,
A is

where R 13 , R 14 , R 15 and R 16 are each independently hydrogen or an alkyl group of 1 to 10 carbon atoms;

in Formula 3,
A 1 and A 2 are each independently a divalent hydrocarbon group of 1 to 20 carbon atoms, which includes or does not include an oxygen atom,
R 17 to R 20 are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms,
L 1 to L 4 are each independently a divalent, trivalent or tetravalent alkylsilyl group which is substituted with an alkyl group of 1 to 10 carbon atoms, or
L 1 to L 4 are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms, or
L 1 and L 2 , and L 3 and L 4 are connected with each other to form a ring of 1 to 5 carbon atoms, wherein the formed ring includes 1 to 3 atoms of one or more heteroatoms selected from the group consisting of N, O and S;

in Formula 4,
R 30 is a monovalent hydrocarbon group of 1 to 30 carbon atoms,
R 31 to R 33 are each independently an alkylene group of 1 to 10 carbon atoms,
R 34 to R 37 are each independently an alkyl group of 1 to 10 carbon atoms, and
g and h are each independently 0, or an integer selected from 1 to 3, where g+h is an integer of 1 or more;

in Formula 5,
A 3 and A 4 are each independently an alkylene group of 1 to 10 carbon atoms,
R 38 to R 41 are each independently an alkyl group of 1 to 10 carbon atoms, or an alkoxy group of 1 to 10 carbon atoms, and
i is an integer of 1 to 30;
(R 43 4-k Sn S—R 44 —Si(OR 45 ) l (R 46 ) 3-l ) k   [Formula 6]

in Formula 6,
R 43 , R 45 and R 46 are each independently an alkyl group of 1 to 10 carbon atoms,
R 44 is an alkylene group of 1 to 10 carbon atoms, and
k is an integer of 1 to 4.

11. The method according to claim 1 , wherein the modifier is a compound represented by the following Formula 7:

in Formula 7,
R 22 and R 23 are each independently an alkylene group of 1 to 20 carbon atoms, or —R 28 [OR 29 ] f —,
R 24 to R 27 are each independently an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms,
R 28 and R 29 are each independently an alkylene group of 1 to 20 carbon atoms,
R 47 and R 48 are each independently a divalent hydrocarbon group of 1 to 6 carbon atoms,
d and e are each independently 0, or an integer selected from 1 to 3, where d+e is an integer of 1 or more, and f is an integer of 1 to 30.

12. The method according to claim 11 , wherein the compound represented by Formula 7 is a compound represented by the following Formula 7a, Formula 7b or Formula 7c:

in Formula 7a, Formula 7b, and Formula 7c,
R 22 and R 23 are each independently an alkylene group of 1 to 20 carbon atoms, or —R 28 [OR 29 ] f —,
R 24 to R 27 are each independently an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms,
R 28 and R 29 are each independently an alkylene group of 1 to 20 carbon atoms,
d and e are each independently 0, or an integer selected from 1 to 3, where d+e is an integer of 1 or more, and f is an integer of 1 to 30.

13. The method according to claim 1 , wherein the conjugated diene-based monomer is one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-2,3-butadiene and 2-halo-1,3-butadiene, wherein halo is a halogen atom.

14. The method according to claim 1 , wherein the organometal compound is present in an amount of from 0.01 mmol to 10 mmol based on 100 g of the conjugated diene-based monomer.

15. The method according to claim 1 , wherein the polymerization conversion rat

Assignees

• Lg Chemical Ltd

Inventors

• Kim Jin Young
• Ko Jun Seok
• Kim No Ma
• Kim Yu Jin
• Son Ki Seok
• Sohn Hae Sung
• Lee Ro Mi
• Lee Sang Mi
• Lee Tae Chui
• Lee He Seung

Classifications

• C08F36/04 Primary

  conjugated · CPC title

• C08K5/17

  Amines; Quaternary ammonium compounds · CPC title

• C08K5/1535

  Five-membered rings · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08C19/22

  Incorporating nitrogen atoms into the molecule · CPC title