Granted Patent B2

US 12,410,263 · App. 17/609,331 · Granted Sep 9, 2025

Inventors: Jeffrey A. Cicerchi (Akron, OH); Terrence E. Hogan (Uniontown, OH); James J. Kuhel, Jr. (Stow, OH)

Assignee: Bridgestone Americas Tire Operations, LLC

C08C19/25B60C1/0016C08F4/545C08K3/013C08K3/04C08K3/36C08K5/0016C08K5/005C08L9/06C08L19/006

Abstract

Claims (48)

1. A modified high-cis polybutadiene polymer having

polymer chains bonded to a residue of a functionalizing compound having formula (I) as follows

where X is a group reactive with the living end polymer chains and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydrides,

R 1 is selected from hydrocarbylene of C 1 -C 20 , wherein each of the foregoing optionally contain one unsaturated carbon-carbon bond,

each R′ is selected from alkoxy of C 1 -C 20 , and

R″ is selected from alkyl of C 1 -C 20 or aryl of C 6 -C 20 ,

wherein each polymer chain is bonded to the residue of the functionalizing compound through the X group, and the modified high-cis polybutadiene polymer has

a cis 1,4-bond content of 92-98%,

an initial Mooney viscosity ML 1+4 at 100° C. of 20-100, and

an aged Mooney viscosity ML 1+4 at 100° C. of no more than 120, wherein the aged Mooney viscosity is determined after aging at 100° C. for 2 days.

2. The modified high-cis polybutadiene polymer of claim 1 , meeting each of the following:

a. has a Mw of 150,000 to 2,000,000 grams/mole;

b. has a Mn of 80,000 to 800,000 grams/mole;

c. has a Mw/Mn of 1.5 to 4; or

d. has an initial Mooney viscosity ML 1+4 at 100° C. of 40 to 70.

3. The modified high-cis polybutadiene polymer of claim 1 , wherein R 1 is selected from hydrocarbylene of C 1 -C 3 .

4. The modified high-cis polybutadiene polymer of claim 1 , wherein R′ is selected from alkoxy of C 1 or C 2 .

5. The modified high-cis polybutadiene polymer of claim 1 , wherein X of formula (I) is an epoxy group.

6. The modified high-cis polybutadiene polymer of claim 5 , wherein X of formula (I) is a glycidoxy group and the polymer chains are bonded to a carbon atom from the epoxy group.

7. The modified high-cis polybutadiene polymer of claim 4 , wherein X of formula (I) is a cyano group.

8. The modified high-cis polybutadiene polymer of claim 5 , wherein R 1 is selected from hydrocarbylene of C 1 -C 3 and R′ is selected from alkoxy of C 1 or C 2 .

9. The modified high-cis polybutadiene polymer of claim 6 , wherein R 1 is selected from hydrocarbylene of C 1 -C 3 and R′ is selected from alkoxy of C 1 or C 2 .

10. The modified high-cis polybutadiene polymer of claim 7 , wherein R 1 is selected from hydrocarbylene of C 1 -C 3 and R′ is selected from alkoxy of C 1 or C 2 .

11. A process for preparing the modified high-cis polybutadiene polymer of claim 1 , the process comprising

A. providing a catalyst system comprising

a. a lanthanide-based catalyst system comprising (i) a lanthanide compound, (ii) an alkylating agent, and (iii) a halogen source, where (iii) may optionally be provided by (i), (ii), or both (i) and (ii),

b. a nickel-based catalyst system comprising (i) a nickel compound, optionally in combination with an alcohol, (ii) an organoaluminum, organomagnesium, organozinc compound, or a combination thereof, and (iii) a fluorine-containing compound or a complex thereof, or

c. a cobalt-based catalyst system, comprising (i) a cobalt compound, (ii) an organo aluminum halide, and (iii) optionally water;

B. using the catalyst system of (A) to polymerize 1,3-butadiene to produce polymer chains with a living end,

C. reacting the living end polymer chains from (B) with the functionalizing compound having formula (I)

thereby producing the modified high-cis polybutadiene polymer

wherein the functionalizing compound is used in a molar ratio of 50:1 to 2:1, the molar ratio based upon the moles of functionalizing compound: moles of primary metal of the catalyst system.

12. The process of claim 11 , wherein the functionalizing compound is used in a molar ratio of 20:1 to 4:1 based upon the moles of functionalizing compound: moles of primary metal of the catalyst system.

13. The process of claim 11 , further comprising:

reacting the modified high-cis polybutadiene from (C) with a stabilizing agent of formula (II) as follows

R 2 n Si(OR 3 ) 4-n

wherein R 2 is selected from the group consisting of C 1 to C 20 alkyl, C 4 to C 10 cycloalkyl, or C 5 to C 20 aromatic groups,

wherein R 3 may be the same as or different from R 2 and is selected from C 1 to C 20 alkyl, C 4 to C 10 cycloalkyl, or C 5 to C 20 aromatic groups, and

n is an integer of 1 to 3

prior to (D),

wherein the stabilizing agent is used in a molar ratio of 0.01:1 to 10:1 based upon the moles of stabilizing agent: moles of functionalizing compound.

14. The process of claim 11 , wherein X of formula (I) is an epoxy group having 2-4 carbon atoms in the epoxy ring.

15. The process of claim 11 , wherein X of formula (I) is a glycidoxy group.

16. The process of claim 11 , wherein X of formula (I) is a cyano group.

17. The process of claim 13 , wherein the stabilizing agent is used with a quenching agent of formula (III) as follows:

R 4 COOH

wherein R 4 is selected from H and the group consisting of C 1 to C 18 alky, and

wherein the quenching agent of formula (III) is used in a molar ratio of 0.1:1 to 10:1, the molar ratio based upon the moles of quenching agent: moles of stabilizing agent.

Assignments (1)

Continuity (2)

References Cited (127)