Copolymer including functional monomer and method of preparing the same

Patent metadata

Field	Value
Publication number	US-11059929-B2
Application number	US-201916369717-A
Country	US
Kind code	B2
Filing date	Mar 29, 2019
Priority date	Mar 29, 2018
Publication date	Jul 13, 2021
Grant date	Jul 13, 2021

Abstract

Provided is a copolymer composed of an aromatic vinyl monomer, a conjugated diene monomer, and a functional monomer including two or more nitrogen atoms and a method of preparing the copolymer.

First claim

What is claimed is:

1. A copolymer, comprising an aromatic vinyl monomer, a conjugated diene monomer, and a functional monomer represented by one or more of Formulas 1 to 3 below:

wherein N is nitrogen,
X is carbon or silicon,
Y is nitrogen, boron, or phosphorus,
R is hydrogen or a C1 to C20 alkyl group,
each of R 1 , R 2 , R 5 , and R 9 is a C1 to C20 saturated or unsaturated hydrocarbon chain, and
each of R 3 , R 4 , R 6 , R 7 , R 8 , R 10 , and R 11 1 is a C1 to C20 alkyl group.

2. The copolymer according to claim 1 , wherein the aromatic vinyl monomer is one selected from the group consisting of styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 5-tert-butyl-2-methylstyrene, tert-butoxystyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, N,N-dimethylaminoethylstyrene, 1-vinyl-5-hexylnaphthalene, 1-vinylnaphthalene, divinylnaphthalene, divinylbenzene, trivinylbenzene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethylether, vinylpyridine, vinylxylene, diphenylethylene, diphenylethylene comprising a tertiary amine, styrene comprising a primary, secondary, or tertiary amine, and a combination of two or more thereof.

3. The copolymer according to claim 1 , wherein the conjugated diene monomer is one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, 3-butyl-1,3-octadiene, octadiene, and a combination of two or more thereof.

4. The copolymer according to claim 1 , wherein at least one terminal of the copolymer is modified with an alkoxysilane compound.

5. The copolymer according to claim 4 , wherein the alkoxysilane compound is represented by Formula 4 below:
(R′O) x SiR″ 4-x   <Formula 4>

wherein R′ is a C1 to C20 alkyl group,
R″ is a C1 to C20 saturated or unsaturated hydrocarbon chain or a C1 to C20 saturated or unsaturated hydrocarbon chain comprising a nitrogen, sulfur, or halogen atom, and
x is an integer of 1 to 3.

6. The copolymer according to claim 4 , wherein the alkoxysilane compound is represented by Formula 5 below:

wherein each of R′ 1 to R′ 8 is a C1 to C20 saturated or unsaturated hydrocarbon chain,
X is carbon, silicon, or nitrogen,
a is 1 or 2,
b is 0, 1, or 2,
each of c and d is an integer of 0 to 3 satisfying b+c+d=3, and
n is 1.

7. The copolymer according to claim 4 , wherein the alkoxysilane compound is represented by Formula 6 below:

wherein each of R′ 9 and R′ 10 is a C1 to C20 saturated or unsaturated hydrocarbon chain or a C1 to C20 saturated or unsaturated hydrocarbon chain comprising a nitrogen, sulfur, or halogen atom,
each of R′ 11 to R′ 13 is a C1 to C20 alkyl group, and
each of e and f is an integer of 0 to 2.

8. The copolymer according to claim 1 , wherein the content of the functional monomer is 0.1 to 10% by weight based on a total weight of the copolymer.

9. A tire rubber composition, comprising the copolymer according to claim 1 .

10. A method of preparing a copolymer, the method comprising:
polymerizing an aromatic vinyl monomer, a conjugated diene monomer, and a functional monomer represented by one or more of Formulas 1 to 3 below in the presence of a solvent, a Lewis base, and a polymerization initiator:

wherein
N is nitrogen,
X is carbon or silicon,
Y is nitrogen, boron, or phosphorus,
R is hydrogen or a C1 to C20 alkyl group,
each of R 1 , R 2 , R 5 , and R 9 is a C1 to C20 saturated or unsaturated hydrocarbon chain, and
each of R 3 , R 4 , R 6 , R 7 , R 8 , R 10 , and R 11 is a C1 to C20 alkyl group.

11. The method according to claim 10 , wherein the solvent is one selected from the group consisting of aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, and a combination of two or more thereof.

12. The method according to claim 10 , wherein the Lewis base is one selected from the group consisting of tetrahydrofuran, di-n-propyl ether, diisopropyl ether, diethyl ether, diethylene glycol dimethyl ether, di-n-butyl ether, ethyl butyl ether, triethylene glycol, 1,2-dimethoxybenzene, ditetrahydrofurylpropane, ditetrahydrofurfurylpropane, ethyltetrahydrofurfurylether, trimethylamine, triethylamine, N,N,N,N-tetramethylethylenediamine, and a combination of two or more thereof.

13. The method according to claim 10 , wherein the polymerization initiator is one selected from the group consisting of an organometallic compound, an amine compound, an imine compound, and a combination of two or more thereof.

14. The method according to claim 10 , wherein a use amount of the polymerization initiator is 0.01 to 10 mmol per 100 g of a total of monomers comprising the aromatic vinyl monomer, the conjugated diene monomer, and the functional monomer.

15. The method according to claim 10 , further comprising modifying at least one terminal of the copolymer with an alkoxysilane compound.

16. The method according to claim 15 , wherein a use amount of the alkoxysilane compound is 0.5 to 5.0 moles per 1 mole of the polymerization initiator.

Assignees

• Korea Kumho Petrochemical Co Ltd

Inventors

• Cho Hanjoung
• Ko Jae Young
• Kim Tae Hee
• Park Cheol Min

Classifications

• C08F236/14 Primary

  containing elements other than carbon and hydrogen · CPC title

• C08F236/10 Primary

  with vinyl-aromatic monomers · CPC title

• C08F212/26

  Nitrogen · CPC title

• B60C1/00 Primary

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

• C08F212/08

  Styrene · CPC title