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8323852 
Journal Article 
Copolymerization of ethylene and vinyl fluoride by (phosphine- bis(arenesulfonate))PdMe(pyridine) catalysts: Insights into inhibition mechanisms 
Shen, Z; Jordan, RF 
2010 
1 
Macromolecules
ISSN: 0024-9297
EISSN: 1520-5835 
43 
21 
8706-8708 
English 
WOS:000283693500003 
A study was conducted to demonstrate that (Li-OPO)-PdMe(L) and 4-(5-nonyl)-py) catalysts catalyzed the copolymerization of ethylene with VF to yield copolymers with a significantly higher level of vinyl fluoride (VF) incorporation than observed for conventional (PO)-PdMe(py) catalysts. These enabled the characterization of unobserved VF placements in the copolymer and provided insights into the mechanism by which VF inhibited polymerization. Ethylene or VF copolymerizations were carried out using the (Li-OPO)-PdMe(L) and 4-(5-nonyl)-py) as the catalysts at 80 °C in toluene or hexanes. The copolymers produced by (Li-OPO)-PdMe(L) in toluene displayed broad molecular weight distributions, indicative of partial fragmentation of the tetranuclear species and similar to results for ethylene homopolymerization. The copolymers produced by 4-(5-nonyl)-py) in toluene displayed narrower molecular weight distributions, indicative of more extensive catalyst fragmentation.