US 12,168,705 B2
Modified high cis polydiene polymer, related methods and rubber compositions
Zengquan Qin, Brentwood, TN (US); and Yuan-Yong Yan, Copley, OH (US)
Assigned to Bridgestone Corporation, Chuo-ku (JP)
Appl. No. 17/438,072
Filed by Bridgestone Corporation, Chuo-ku (JP)
PCT Filed Mar. 10, 2020, PCT No. PCT/US2020/021864
§ 371(c)(1), (2) Date Sep. 10, 2021,
PCT Pub. No. WO2020/185761, PCT Pub. Date Sep. 17, 2020.
Claims priority of provisional application 62/816,130, filed on Mar. 10, 2019.
Prior Publication US 2022/0185931 A1, Jun. 16, 2022
Int. Cl. C08F 8/30 (2006.01); B60C 1/00 (2006.01); C08F 4/54 (2006.01); C08F 236/06 (2006.01); C08K 3/04 (2006.01)
CPC C08F 236/06 (2013.01) [B60C 1/0016 (2013.01); C08F 4/545 (2013.01); C08F 8/30 (2013.01); C08K 3/04 (2013.01); C08F 2438/00 (2013.01); C08F 2810/40 (2013.01)] 20 Claims
 
1. A process for preparing a modified high cis polydiene polymer comprising:
a. providing 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. using the catalyst system of (a) to polymerize a quantity of conjugated diene monomer to produce polymer chains with a living end;
c. reacting the living end polymer chains from (b) with a functionalizing compound selected from:
i.

OG Complex Work Unit Chemistry
wherein n is an integer of 0 to 16, or
ii.

OG Complex Work Unit Chemistry
wherein R1 is selected from H and hydrocarbyl of C1-C20, and R2 is selected from H and hydrocarbyl of C1-C20,
thereby producing an intermediary product including polymer chains end functionalized with a residue from the first functionalizing compound;
d. coupling the intermediary product from (c) using a coupling agent selected from the group consisting of silicon halides,
thereby producing a modified high cis polydiene polymer having a cis 1,4-bond content of at least 92%, and a Mooney viscosity ML1+4 at 100° C. of 40-80.