End group functionalization agents for polydiene

Patent metadata

Field	Value
Publication number	US-10919989-B2
Application number	US-201816166939-A
Country	US
Kind code	B2
Filing date	Oct 22, 2018
Priority date	Oct 20, 2017
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

Abstract

The present invention relates to a modified polymer having the structure of Formula (I) and Formula (IV):

wherein A,

R 1 , R 2 , R 3 , a, and n are as described herein and

wherein

R, R′, R″, x, and k are as described herein and methods for preparation thereof. The present invention also relates to a compound having the structure of Formula (II):

wherein A, R 1 , R 2 , R 3 , a, and n are as described herein. The present invention also relates to a process for polymerizing unsaturated hydrocarbon monomers.

First claim

What is claimed:

1. A modified polymer having the structure of Formula (I):

wherein

is a polymer;
A is selected from the group consisting of

C 1-15 alkyl, C 1-15 alkylene, C 3-8 cycloalkyl, aryl, arylene, and

wherein C 1-15 alkyl, C 1-15 alkylene, C 3-8 cycloalkyl, aryl, and arylene can be optionally substituted from 1 to 4 times with a substituent independently selected from the group consisting of H, halogen, C 1-6 alkyl, and —NR 7 R 8 ;

is a point of attachment of A to

group;
R 1 is C 1-6 alkyl;
R 2 is H or C 1-6 alkyl;
R 3 is H or C 1-6 alkyl;
R 4 is C 1-6 alkyl;
R 5 is H or C 1-6 alkyl;
R 6 is H or C 1-6 alkyl;
R 7 is H or C 1-6 alkyl;
R 8 is H or C 1-6 alkyl;
R 9 is C 1-6 alkyl;
R 10 is C 1-6 alkyl;
X 1 is C 1-6 alkylene;
X 2 is C 1-15 alkylene;
Y is O or N;
Z is H, R 9 , or Si(R 10 ) 3 ;
a is 0 to 2;
b is 1 or 2; and
n is 1 to 3.

2. The modified polymer of claim 1 , wherein the polymer of Formula (I) has Formula (Ia):

wherein
A is selected from the group consisting of

C 1-15 alkyl, C 3-8 cycloalkyl, and aryl, wherein C 1-15 alkyl, C 3-8 cycloalkyl, and aryl can be optionally substituted from 1 to 4 times with a substituent independently selected from the group consisting of H, halogen, C 1-6 alkyl, and —NR 7 R 8 .

3. The modified polymer of claim 2 having the structure:

4. The modified polymer of claim 2 having the structure:

5. The modified polymer of claim 1 , wherein the polymer

has a 1,4-cis content of 15 to 99%.

6. The modified polymer of claim 1 , wherein the polymer

is a polymer of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, or myrcene.

7. The modified polymer of claim 1 , wherein the polymer

is a polymer of isoprene.

8. A process for polymerizing unsaturated hydrocarbon monomers, said process comprising:
providing unsaturated hydrocarbon monomers;
providing a compound of Formula (II):

wherein
A is selected from the group consisting of

C 1-15 alkyl, C 1-15 alkylene, C 3-8 cycloalkyl, aryl, arylene, and

wherein C 1-15 alkyl, C 1-15 alkylene, C 3-8 cycloalkyl, aryl, and arylene can be optionally substituted from 1 to 4 times with a substituent independently selected from the group consisting of H, halogen, C 1-6 alkyl, and —NR 7 R 8 ;

is a point of attachment of A to

group;
R 1 is C 1-6 alkyl;
R 2 is H or C 1-6 alkyl;
R 3 is H or C 1-6 alkyl;
R 4 is C 1-6 alkyl;
R 5 is H or C 1-6 alkyl;
R 6 is H or C 1-6 alkyl;
R 7 is H or C 1-6 alkyl;
R 8 is H or C 1-6 alkyl;
R 9 is C 1-6 alkyl;
R 10 is C 1-6 alkyl;
X 1 is C 1-6 alkylene;
X 2 is C 1-15 alkylene;
Y is O or N;
Z is H, R 9 , or Si(R 10 ) 3 ;
a is 0 to 2;
b is 1 or 2;
n is 1 to 3; and
providing a catalyst selected from the group consisting of: (1) a mixture of (A) a compound of Formula M 1 A 1 3 ; (B) a halogen containing compound; and (C) an organometallic compound, wherein M 1 is a lanthanide metal; A 1 is C 8-20 carboxylate; (2) a mixture of (A) a compound of Formula M 2 (HA 2 )A 2 3 ; (B) a halogen containing compound; and (C) an organometallic compound, wherein M 2 is a lanthanide metal; A 2 is C 8-20 carboxylate; (3) a compound of Formula Li-Alk, wherein Alk is C 1-6 alkyl; and (4) a compound of Formula (III): MC(SiHAlk 2 ) 3 (R 11 ) 2 (III), wherein M is a lanthanide or a transition metal; Alk is C 1-6 alkyl; R 11 is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate, alkoxide, amide, BR 12 4 , AlR 12 4 , or alkyl aluminate; R 12 is independently selected at each occurrence thereof from the group consisting of H, C 6 F 5 , phenyl, and C 1-6 alkyl; and
polymerizing the unsaturated hydrocarbon monomers in the presence of the catalyst and the compound of Formula (II) under conditions effective to produce the modified polymer.

9. The process of claim 8 , wherein the catalyst is a mixture of (A) a compound of Formula M 1 A 1 3 ; (B) a halogen containing compound; and (C) an organometallic compound, wherein M 1 is a lanthanide metal; A 1 is C 8-20 carboxylate.

10. The process of claim 8 , wherein the catalyst is a mixture of (A) a compound of Formula M 2 (HA 2 )A 2 3 ; (B) a halogen containing compound; and (C) an organometallic compound, wherein M 2 is a lanthanide metal; A 2 is C 8-20 carboxylate.

11. The process of claim 8 , wherein the catalyst is a compound of Formula Li-Alk, wherein Alk is C 1-6 alkyl.

12. The process of claim 8 , wherein the catalyst is a compound of Formula (III): MC(SiHAlk 2 ) 3 (R 11 ) 2 (III), wherein M is a lanthanide or a transition metal; Alk is C 1-6 alkyl; R 11 is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate, alkoxide, amide, BR 12 4 , AlR 12 4 , or alkyl aluminate; R 12 is independently selected at each occurrence thereof from the group consisting of H, C 6 F 5 , phenyl, and C 1-6 alkyl.

13. The process of claim 8 , wherein the compound of Formula (II) has Formula (IIa):

wherein
A is selected from the group consisting of

C 1-15 alkyl, C 3-8 cycloalkyl, and aryl, wherein C 1-15 alkyl, C 3-8 cycloalkyl, and aryl can be optionally substituted from 1 to 4 times with a substituent independently selected from the group consisting of H, halogen, C 1-6 alkyl, and —NR 7 R 8 .

14. The process of claim 13 , wherein the compound of Formula (IIa) has the following structure:

Assignees

• Univ Iowa State Res Found Inc
• Kumho Petrochemical

Inventors

• Sadow Aaron David
• Schmidt Bradley M
• Kwag Gwanghoon
• Lee Hanbaek
• Kang Dong Eun

Classifications

• C08F136/08

  Isoprene · CPC title

• C08F136/06

  Butadiene · CPC title

• C08L9/06

  Copolymers with styrene · CPC title

• C08C19/44

  of polymers containing metal atoms exclusively at one or both ends of the skeleton · CPC title

• C08F236/06

  Butadiene · CPC title