End group functionalization agents for polydiene

Patent metadata

Field	Value
Publication number	US-11795243-B2
Application number	US-202117145933-A
Country	US
Kind code	B2
Filing date	Jan 11, 2021
Priority date	Oct 20, 2017
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

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 (IV):

wherein
each indicates a bond with cis and/or trans geometric isomerism;

is a polymer of formula

R is H or C 1-6 alkyl;
R′ is selected from the group consisting of H and —NR a R b ;
R″ is H or C 1-6 alkyl;
R a is H or C 1-6 alkyl;
R b is H or C 1-6 alkyl;
W is a repeating unit of the polymer;
m is 1000 to 55000;
k is 1 or 500; and
x is 0 to 3.

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

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

3. 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.

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

is a polymer of isoprene.

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

is a polymer of butadiene.

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

wherein
R is H or C 1-6 alkyl;
R′ is selected from the group consisting of H, C 1-6 alkyl, —OC 1-6 alkyl, and —NR a R b ,
R″ is H or C 1-6 alkyl;
R a is H or C 1-6 alkyl;
R b is H or C 1-6 alkyl; and
x is 0 to 3;
providing a catalyst selected from the group consisting of: (1) 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; and (2) 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 (V) under conditions effective to produce the modified polymer.

7. The process of claim 6 , wherein the modified polymer has 1,4-cis content of 15 to 99%.

8. The process of claim 6 , wherein the modified polymer has more than 90% cis-content.

9. The process of claim 6 , wherein the modified polymer has a molecular weight of 10,000 to 4,000,000.

10. The process of claim 6 , wherein the modified polymer has a Mooney viscosity of 10 to 100.

11. The process of claim 6 , 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.

12. The process of claim 6 , 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.

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

14. The process of claim 6 , 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.

Assignees

• Univ Iowa State Res Found Inc
• Kumho Petrochemical

Inventors

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

Classifications

• C08C19/25 Primary

  Incorporating silicon atoms into the molecule · CPC title

• C08C19/44

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

• C08F136/06

  Butadiene · CPC title

• C08F136/08

  Isoprene · CPC title

• C08F236/06

  Butadiene · CPC title