Method of polymerization

C - Chemistry – Metallurgy – 08 – F

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402/444, 252/79

C08F 4/12 (2006.01) C08F 36/06 (2006.01) C08F 136/06 (2006.01)

Patent

CA 1069107

Abstract of the Disclosure A method of polymerization of butadiene to form polymers with a high (greater than 90 percent) content of cis-1,4 configuration which comprises a process for the polymerization of butadiene under solution polymeriza- tion conditions to form a polybutadiene having a high proportion of butadiene units in the cis-1,4-conf?guration comprising contacting butadiene with a catalyst consisting essentially of (1) an organoaluminum compound (A1) selected from the group consisting of triisobutylaluminum and tri- n-butylaluminum, (2) an organonickel compound (Ni), and (3) a fluorinated mixture wherein the improvement com- prises utilizing a mixture of hydrogen fluoride atherate (HF?Eth) and boron trifluoride etherate (BF3?EtH) where the molar ratio of fluoride to aluminum (F/A1) (total fluoride from BF3?Eth and HF?Eth) ranges upward from 3.0/1 to 20/1 when the mole percent of HF with respect to the total fluoride ranges from about 5 percent to 50 percent and when the mole percent of HF with respect to the total fluoride ranges from 50.1 percent to 95 percent, then for every one percent increase of HF in said hydrogen fluoride etherate and boron trifluoride etherate mixture, the F/A1 molar ratio starting at 20/1, has to decrease by 0.377, wherein the mole ratio of the organoaluminum compound (A1) to the organonickel compound (Ni) ranges from about 10/1 to about 60/1.

250470

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