Continuous solution copolymerization of ethylene and octene-1 with constrained geometry metallocene catalyst

Randomly Functionalized Polyethylenes: In Quest of Avoiding Catalyst Deactivation

“…By plotting F ( f – 1)/ f versus F 2 / f , where F = [ethylene]/[10-undecen-1-ol] in the feed and f = [ethylene]/[10-undecen-1-ol] in the copolymer, the reactivity rates of ethylene ( r ethylene = 28.9) and 10-undecen-1-ol ( r C 11 OH = 0.49) were obtained (Figure S4). The r C 11 OH value is unusually high and similar to the r 1‑decene found for the expanded constrained geometry zirconium catalyst ( r ethylene = 14.9; r 1‑decene = 0.49), Me 2 Si­(η 1 -C 29 H 36 )­(η 1 -N- t -Bu)­ZrCl 2 ·OEt 2 , reported by Miller and co-workers and notably larger than the r 1‑octene values for the CGC catalyst, Me 2 Si­(η 5 -C 5 Me 4 )­(η 1 -N- t -Bu)­TiCl 2 ( r ethylene = 7.90; r 1‑octene = 0.10) …”

Long-Chain Branching with Metallocene Catalysts: Is a Purely Kinetic Mechanism for Terminal Branching Sufficient?

“…As pointed out by them, a mechanism involving macromer formation, diffusion away from the catalyst site, and re‐incorporation into a growing polymer chain is unlikely in gas phase polymerization, unless additional hypotheses regarding this mechanism are made. Similar conclusions were drawn by Wang et al for the solution polymerization of ethylene and 1‐octene 14…”

Sterically expanded CGC catalysts: substituent effects on ethylene and α-olefin polymerization

“…Note that the value for r 1-decene = 0.49 is about an order of magnitude larger than that for typical metallocenes; for example, ethylene bis(indenyl)ZrCl 2 /MAO gives r ethylene = 45 and r 1-octene = 0.05. 16 Our obtained value of r 1-decene = 0.49 is also notably larger than that reported for 1-octene with the Dow-Exxon CGC 1/MAO (r ethylene = 7.90 and r 1-octene = 0.10) 17 and even that reported for propylene with 1/MAO (r ethylene = 4.33 and r propylene = 0.38). 18 Adding to the impressive behavior…”