Synthesis of Palladium Complexes with an Anionic P∼O Chelate and Their Use in Copolymerization of Ethene with Functionalized Norbornene Derivatives:  Unusual Functionality Tolerance

Abstract

A series of anionic P∼O ligands and corresponding palladium-allyl complexes have been synthesized. The latter, along with palladium species formed in situ, were employed for the copolymerization of ethene with functionalized norbornene derivatives. The formed copolymers had high norbornene content (>40 mol %). The systems are highly tolerant of reactive functionalities, and the copolymerizations can even be carried out in the presence of water.

Investigation of Steric and Electronic Factors of (Arylsulfonyl)phosphane‐Palladium Catalysts in Ethene Polymerization

“…The six-membered ring Pd1-P1-C131=C132-S1-O11-adopts a half-boat conformation, with C111 and O13 in pseudoaxial positions and C121 and O12 in pseudoequato- rial positions. This half-boat conformation has been reported for the majority of aryl sulfonate catalysts, [11,14,17,23] except for bulky aryl groups or when pyridine is replaced by DMSO. [12,15] The complete characterization of catalysts 3Pd and 4Pd is complicated by the fact that each rotamer reacts to give a separate catalyst, thus resulting in a doubling of all phosphane resonances ( Figure 3).…”

“…gand were then disclosed by Hearley et al, [6] Goodall et al, [7,8] Kochi et al, [9,10] Liu et al, [11] Skupov et al, [12] Luo et al, [13] Vela et al, [14] and most recently Guironnet et al [15] Among those reports, acrylate copolymerization with ethene was mentioned by Goodall, [7,8] Skupov, [12] and Guironnet. [15] These studies employ the catalyst [(oAr 2 PC 6 H 4 SO 3 )PdMe(L)] with Ar = o-OMePh, which corresponds to the ligand originally presented by Drent.…”

“…[15] These studies employ the catalyst [(oAr 2 PC 6 H 4 SO 3 )PdMe(L)] with Ar = o-OMePh, which corresponds to the ligand originally presented by Drent. [5] The role of the ancillary ligand L (L = pyridine, [12,16] lutidine, [17] DMSO, [15] or allyl group [11] ) on the catalytic activity has been studied in detail. However, at this time, little is known on the influence of the arylphosphane sulfonate structure.…”

Metal catalysts for the vinyl/addition polymerization of norbornene

“…Hence, a catalyst for the copolymerization of ethene with functionalized norbornenes most be both tolerant of functional groups and resistant to ␤-hydrogen elimination. Yet in particular with nickel-based systems for the copolymerization of ethene with functionalized norbornenes the extent of incorporation of the norbornene derivative monomer is less than 25 mol% [75].…”

High‐Impact Polyamide Composites with Linear Ethylene–Norbornene Anhydride Copolymers from Insertion Polymerization

“…Additionally, low polymerization activities are often observed due to reversible intra-and intermolecular deactivation by coordination of the functional groups present to the palladium center. Intriguingly, norbornene [13,14] and some of its functional derivatives, [15] such as norbornene anhydride, [16] are exceptions to these trends observed for other polar monomers such as acrylic acid, [17] maleic anhydride, [16] or acrylates. [6,18,19] Chain transfer is even less pronounced after the incorporation of a norbornene anhydride unit into the growing chain than for ethylene leading to an increase of molecular weight with increasing norbornene anhydride content in the copolymer.…”