This invention is based upon the unexpected discovery that alkylated
diphenylamines can be used in conjunction with nickel based catalyst
systems which contain (a) an organonickel compound, (b) an organoaluminum
compound, and (c) a fluorine containing compound to produce
cis-1,4-polybutadiene having reduced molecular weight and an increased
level of branching. This results in the cis-1,4-polybutadiene exhibiting
good processability without sacrificing cold flow characteristics.
Additionally, the alkylated diphenylamine which remains in the rubber
acts in a manner which provides it with antioxidant protection. In other
words, the use of alkylated diphenylamines accomplishes the three major
objectives that are realized by employing para-styrenated diphenylamines
(reduced molecular weight, regulated polymer macrostructure through
branching and antidegradant protection). However, the utilization of
alkylated diphenylamines, unlike para-styrenated diphenylamines, offers
the additional advantage of being soluble in aliphatic solvents. By
virtue of this increased level of solubility in aliphatic solvents, such
as hexane, alkylated diphenylamines can be employed at greatly reduced
levels of aromatic solvents. Likewise, when mixed catalyst streams
containing alkylated diphenyl amines are combined precipitation is
minimized compared to para-styrenated diphenylamine significantly
improving issues related to fouling. The subject invention more
specifically discloses a process for producing cis-1,4-polybutadiene
having a reduced molecular weight and improved processability which
comprises polymerizing 1,3-butadiene in the presence of (a) an
organonickel compound, (b) an organoaluminum compound, (c) a fluorine
containing compound, and (d) an alkylated diphenylamine; wherein the
alkylated diphenylamine has alkyl groups that contain from 2 to 18 carbon
atoms, and wherein the organoaluminum compound and the fluorine
containing compound are brought together in the presence of the alkylated
diphenylamine.