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Butadiene polymerization with nickel compounds: Effect of cocatalysts
Author(s) -
Throckmorton M. C.
Publication year - 1991
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1991.070421120
Subject(s) - polymerization , boron trifluoride , chemistry , alkyl , polymer chemistry , polybutadiene , nickel , polymer , copolymer , catalysis , organic chemistry
The preparation of a high cis ‐1,4‐polybutadiene, using a novel ternary catalyst system composed of triethylaluminum, a soluble nickel compound, and boron trifluoride diethyl etherate has been reported in the literature. The present paper reports the polymerization results obtained when the triethylaluminum was replaced with other alkylaluminums and the BF 3 · Et 2 O was replaced with other BF 3 complexes or HF · Et 2 O. When utilizing BF 3 · Et 2 O, both the polymerization rate and the polymer DSV decreased significantly as the length of the alkyl group in the alkylaluminum increased from C 1 to C 6 . However, the length and nature of the alkyl group had virtually no effect when utilizing BF 3 · phenolate (BF 3 · 2C 6 H 5 OH) and only a small effect with HF · Et 2 O; although the length of the alkyl group had no significant effect when using BF 3 complexes of aromatic aldehydes, the branched alkyl groups gave greater polymerization rates than did the corresponding n ‐alkyls. In summary, the strongly acidic complexes, BF 3 · phenolate and HF · etherate, promoted rapid polymerization when employed with any of the alkylaluminums. However, with other BF 3 complexes, the alkylaluminum selected had an important influence upon either the conversion and/or the polymer DSV.