Kinetic Study of the Ring-Opening Metathesis Polymerization of Ionically Functionalized Cyclooctatetraenes

Abstract

The ring-opening metathesis polymerizations of alkylammonium and sulfonate functionalized cyclooctatetraenes (RCOT, R ) CH 2CH2SO3TMA or CH2CH2NMe3OTf, OTf ) CF3SO3 -, TMA ) Me4N + ) with the well-defined tungsten catalyst WdCH(o-C6H4OMe)(NC6H5)[OCCH3(CF3)2]2(THF) (THF ) tetrahydrofuran) were investigated. The polymerizations exhibited first-order decay in monomer concentration and slow initiation relative to propagation, and for COTCH2CH2SO3TMA where studies were possible, molecular weights largely independent of the extent of the reaction and initial reaction conditions. The central kinetic feature was the observation of a pseudo-first-order rate constant inversely proportional to the initial monomer concentration, suggesting some form of inhibition. Furthermore, the polymerization of COTCH 2CH2NMe3OTf is inhibited by the addition of TBAOTf (TBA ) Bu4N + ). The apparent inhibition is discussed in terms of the potential for ion pairing or anion coordination to the catalyst center.

The controlled homogeneous organic solution polymerization of new hydrophilic cationic exo‐7‐oxanorbornenes via ROMP with RuCl2(PCy3)2CHPh in a novel 2,2,2‐trifluoroethanol/methylenechloride solvent mixture

“…The target ionic functionality was introduced into the resulting (co)polymers via the trifluoroacetic acid deprotection of the t BOC‐protected primary amine species or via the base hydrolysis of the anhydride residues. Lonergan et al27, 28 have described the direct polymerization of cationic and anionic cyclooctatetraene derivatives using a Schrock W‐based initiator in chloroform or methylene chloride. The polymerizations did not remain homogeneous due to the insolubility of the resulting ionic polyacetylenes in the polymerization solvents.…”

Effect of Electrical Conductivity Through the Bulk Doping of the Product of Titanocene Dichloride and 2-Nitro-1,4-phenylenediamine

“…We have just begun investigating the results of polymer doping. While there are a number of different doping procedures employed in the production of conducting polymers, the most widely employed is the exposure of the polymeric material, often in a compacted disk, to elemental iodine vapors either as a vapor or as part of a mixture as we have done in the present study [ 1 , 7 , 8 , 9 , 10 , 11 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ]. We studied the effects of doping of over 50 products.…”

“…The importance of this effort was recognized by the awarding of the Nobel Prize in 2000 to MacDiarmid, Heeger, and Shirakawa for their work with polyacetylene [ 1 , 2 , 3 , 4 , 5 , 6 ]. Conductivity is dependent on the micro- or fine structure of the fibrils, doping agent, extent, technique, and aging of the sample as well as other factors so it is complex [ 7 , 8 , 9 , 10 , 11 , 12 , 13 ].…”

Kinetic Study of the Ring-Opening Metathesis Copolymerization of Ionic with Nonionic Cyclooctatetraene Derivatives To Yield Polyacetylene Ionomers

“…The initial rate in these systems shows a zero-order dependence on the initial monomer concentration, whereas the monomer decays show a first-order dependence on monomer concentration. 46 In previous experiments on the properties of isolated copolymers, 9 polymerizations were intentionally quenched after less than 20% conversion in an effort to balance yield with compositional uniformity. The reactivity ratios and kinetic data now provide for an estimate of the compositional uniformity expected in these polymers.…”

“…Such studies are needed to understand monomer distribution and identify appropriate reaction conditions for the fabrication of polymers with acceptable levels of compositional uniformity. In the homopolymerization of ionically functionalized RCOTs, the presence of ionizable groups strongly influences the polymerization mechanics, 46 and they are expected to have a similarly strong influence on copolymerization.…”