Copolymer, method of preparing the same, and rubber composition including the same

Patent metadata

Field	Value
Publication number	US-11820847-B2
Application number	US-202217857768-A
Country	US
Kind code	B2
Filing date	Jul 5, 2022
Priority date	Dec 20, 2021
Publication date	Nov 21, 2023
Grant date	Nov 21, 2023

Abstract

An embodiment of the present specification provides a method of preparing a copolymer, which includes steps of: (a) adding a polymerization initiator to a monomer mixture including an aromatic vinyl-based monomer, a first conjugated diene-based monomer, and a farnesene monomer to initiate a reaction; and (b) adding a second conjugated diene-based monomer.

First claim

What is claimed is:

1. A method of preparing a copolymer, comprising steps of:
(a) adding a polymerization initiator to a monomer mixture including an aromatic vinyl-based monomer, a first conjugated diene-based monomer, and a farnesene monomer to initiate a reaction;
(b) adding a second conjugated diene-based monomer; and
(c) adding a compound represented by the following Chemical Formula 1 or Chemical Formula 2:

in Chemical Formula 1 and Chemical Formula 2,
R 1 to R 7 are each one of C 1 to C 20 saturated or unsaturated hydrocarbon chains,
R 8 is hydrogen (H) or one of C 1 to C 20 saturated or unsaturated hydrocarbon chains,
R 9 to R 13 are each one of C 1 to C 20 saturated or unsaturated hydrocarbon chains,
X is carbon (C), silicon (Si), or nitrogen (N),
Y is oxygen (O) or nitrogen (N),
a is an integer of 0 to 2,
b, c, and d are each an integer of 0 to 3 and satisfy b+c+d=3,
e, f, and g are each an integer of 0 to 2,
n is an integer of 1 to 200, and
m is an integer of 0 to 2.

2. The method of claim 1 , wherein the aromatic vinyl-based 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 including a tertiary amine, styrene including a primary, secondary, or tertiary amine, and a combination of two or more thereof.

3. The method of claim 1 , wherein the first conjugated diene-based monomer and the second conjugated diene-based monomer are each 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 method of claim 1 , wherein a weight ratio of the aromatic vinyl-based monomer, the first conjugated diene-based monomer, and the farnesene monomer in the monomer mixture is 20 to 50:30 to 70:10 to 30.

5. The method of claim 1 , wherein the second conjugated diene-based monomer is added in an amount of 1 to 30 parts by weight based on 100 parts by weight of the first conjugated diene-based monomer.

6. A method of preparing a copolymer, comprising steps of:
(a) adding a polymerization initiator to a monomer mixture including an aromatic vinyl-based monomer, a first conjugated diene-based monomer, and a farnesene monomer to initiate a reaction;
(b) adding a second conjugated diene-based monomer; and
adding a terminal-modifying compound,
wherein the terminal-modifying compound is one selected from the group consisting of piperidine, 1-[(4-ethylphenyl)methyl]-pyrrolidine, 1-(4-vinylbenzyl)pyrrolidine, N1-(3-(dimethylamino)propyl)-N3,N3-dimethyl-N1-(4-vinylbenzyl)propane-1,3-diamine, N1-(3-(dimethylamino)propyl)-N3,N3-dimethyl-N1-(4-vinylphenethyl)propane-1,3-diamine, N1-(2-(dimethylamino)ethyl)-N2,N2-dimethyl-N1-(4-vinylbenzyl)ethane-1,2-diamine, N1-(3-(diethylamino)propyl)-N3,N3-diethyl-N1-(4-vinylbenzyl)propane-1,3-diamine, triethoxysilylpropyldiethylamine, 3-glycidoxypropyldimethyldimethoxysilane, dimethyldichlorosilane, trimethylchlorosilane, methyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, and a combination of two or more thereof.

7. A copolymer comprising an aromatic vinyl-based monomer, a conjugated diene-based monomer, and a farnesene monomer and having an aromatic vinyl-based block content of less than 1 wt %, wherein at least one end of the copolymer is modified with a compound represented by the following Chemical Formula 1 or Chemical Formula 2:

in Chemical Formula 1 and Chemical Formula 2,
R 1 to R 7 are each one of C 1 to C 20 saturated or unsaturated hydrocarbon chains,
R 8 is hydrogen (H) or one of C 1 to C 20 saturated or unsaturated hydrocarbon chains,
R 9 to R 13 are each one of C 1 to C 20 saturated or unsaturated hydrocarbon chains,
X is carbon (C), silicon (Si), or nitrogen (N),
Y is oxygen (O) or nitrogen (N),
a is an integer of 0 to 2,
b, c, and d are each an integer of 0 to 3 and satisfy b+c+d=3,
e, f, and g are each an integer of 0 to 2,
n is an integer of 1 to 200, and
m is an integer of 0 to 2.

8. A rubber composition comprising the copolymer of claim 7 a filler.

9. A copolymer comprising an aromatic vinyl-based monomer, a conjugated diene-based monomer, and a farnesene monomer and having an aromatic vinyl-based block content of less than 1 wt %, wherein at least one end of the copolymer is modified with a terminal-modifying compound, and
the terminal-modifying compound is one selected from the group consisting of piperidine, 1-[(4-ethylphenyl)methyl]-pyrrolidine, 1-(4-vinylbenzyl)pyrrolidine, N1-(3-(dimethylamino)propyl)-N3,N3-dimethyl-N1-(4-vinylbenzyl)propane-1,3-diamine, N1-(3-(dimethylamino)propyl)-N3,N3-dimethyl-N1-(4-vinylphenethyl)propane-1,3-diamine, N1-(2-(dimethylamino)ethyl)-N2,N2-dimethyl-N1-(4-vinylbenzyl)ethane-1,2-diamine, N1-(3-(diethylamino)propyl)-N3,N3-diethyl-N1-(4-vinylbenzyl)propane-1,3-diamine, triethoxysilylpropyldiethylamine, 3-glycidoxypropyldimethyldimethoxysilane, dimethyldichlorosilane, trimethylchlorosilane, methyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, and a combination of two or more thereof.

10. A rubber composition comprising the copolymer of claim 9 and a filler.

Assignees

• Korea Kumho Petrochemical Co Ltd

Inventors

• Kim Tae Hee
• Ko Jae Young

Classifications

• C08F236/22 Primary

  the radical having three or more carbon-to-carbon double bonds · CPC title

• C08F8/42

  Introducing metal atoms or metal-containing groups · CPC title

• C08F297/042

  using a polyfunctional initiator · CPC title

• C08F236/06 Primary

  Butadiene · CPC title

• C08F236/10 Primary

  with vinyl-aromatic monomers · CPC title