η5-Cyclopentadienylpalladium(II) complexes: Synthesis, characterization and use for the vinyl addition polymerization of norbornene and the copolymerization with 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene

Switchable Polymerization of Norbornene Derivatives by a Ferrocene‐Palladium(II) Heteroscorpionate Complex

“…Vinyl polynorbornenes are important materials for optical applications due to their excellent thermal stability, high glass transition temperatures, small birefringence, and dielectric loss However, polynorbornenes are brittle, even at high molecular weights, display poor adhesion to common substrates, poor solubility in common organic solvents, and cannot be melt processed due to decomposition . Modifying the norbornene monomers with functional groups increases the solubility of the resulting polymers and improves their processability . The substitution of norbornenes, typically at the 5‐position, can be achieved via a Diels–Alder reaction, in some cases, directly from dicyclopentadiene and a dienophile .…”

“…Amongst transition metal catalysts, palladium‐based systems are highly active toward norbornene polymerization and produce high molecular weight vinyl polynorbornenes , . Most palladium catalysts feature bidentate or monodentate supporting ligands since an open coordination sphere is necessary for monomer coordination , , , . Commonly employed systems also require the use of strong Lewis acids/alkylating reagents (i.e.…”

Highly efficient vinylic addition polymerization of 5-vinyl-2-norbornene using benzylic palladium complexes as precatalysts

“…7,17 VAcopolymers of VNB with norbornene have also been synthesized using palladium or nickel catalysts with low incorporation of VNB. 18 The use of certain zirconocene derivatives allows to co-polymerize VNB and ethylene or propylene without the involvement of the exocyclic double bond of VNB; however the incorporation of VNB in the copolymers is low.…”

Synthesis, characterization, rheological and thermal behavior of metallocene ethylene − norbornene copolymers with low norbornene content using pentafluorophenol modified methylaluminoxane

“…In particular, the vinyl addition route using transition metal catalysts seems to be a promising procedure because the ring structure of norbornene remains unreacted and only the double bond gets involved in a chemical reaction. Furthermore, the desired properties of the copolymer can be achieved by altering the co‐monomer composition on the one hand and the copolymer's microstructure on the other hand through appropriate catalyst selection . Among the transition metal catalysts, ansa ‐metallocene catalysts lead to the synthesis of EN copolymers with uniform co‐monomer composition and a variety of microstructures according to the catalyst's structural features, i.e.…”