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Polymerization of olefins and polar monomers catalyzed by bis(imino)Ni(II)/dibutylmagnesium/alkylaluminium halide systems
Author(s) -
Chien James C W,
Fernandes Susete,
Correia Sandra G,
Rausch Marvin D,
Dickson L Charles,
Marques Maria M
Publication year - 2002
Publication title -
polymer international
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.592
H-Index - 105
eISSN - 1097-0126
pISSN - 0959-8103
DOI - 10.1002/pi.966
Subject(s) - polymer chemistry , copolymer , ethylene , polymerization , monomer , chemistry , acrylonitrile , methyl vinyl ketone , catalysis , acenaphthene , organic chemistry , polymer , pyrene
[Bis( N , N ′‐dimesitylimino)acenaphthene]dibromonickel ( 1 ) when activated with diethylaluminium chloride (DEAC) is a very active catalyst for ethylene homopolymerization. The activity ( A E ) of 1 /100 DEAC is twenty times greater than that of 1 /100 MAO and of the same order of magnitude as 1 /2000 MAO. In the case of homopolymerization of propylene the highest activity ( A P ) was obtained at a ratio of 25/15 for Al DEAC /Ni. Trialkylaluminium compounds were also found to act as cocatalysts for 1 . The PE synthesized with four different cocatalysts was found by 13 C NMR to have dissimilar branching distributions. 1 /DEAC shows no activity for the polymerization of proximately substituted polar monomers. The introduction of dibutylmagnesium, (DBM) activates the 1 /DEAC system to copolymerize ethylene and a number of proximately substituted polar monomers. Compared with the 1 /MAO/monomer.AlR 3 catalyst system the former is three times more active for copolymerization of 5‐hexene‐1‐ol or 10‐undecen‐1‐oic acid with ethylene. The activity of copolymerization is 1 /24, 1 /5 and 1 /2 as active as homopolymerization, respectively, in the case of methyl vinyl ketone, vinyl acetate and ϵ‐caprolactam. In the case of tetrahydrofuran/ethylene, the 1 /MAO catalyst produced copolymers using AlR 3 pretreated THF whereas the 1 /DEAC/DBM catalyst produces homopolyethylene only. No polymerization occurred with an acrylonitrile/ethylene mixture in the presence of 1 /DBM/DEAC catalyst. © 2002 Society of Chemical Industry