Effect of the Halide Counterion in the ROMP of exo‐Benzyl‐[2‐(3,5‐dioxo‐10‐oxa‐4‐aza‐tricyclo[5.2.1.0^2,6]dec‐8‐en‐4‐yl)ethyl]dimethyl ammonium Bromide/Chloride

Abstract

Effect of the Halide Counterion in the ROMP of exo-Benzyl-[2-(3,5-dioxo-10-oxa-4-azatricyclo[5.2.1.0 2,6 ]dec-8-en-4-yl)ethyl]dimethyl ammonium Bromide/Chloride

ROMP synthesis of novel thermo‐, pH‐, and salt‐responsive (co)polymers containing the morpholino functional group

“…The copolymerization of M1 with M2 was accomplished in a solvent mixture of CH 2 Cl 2 and 2,2,2,‐TFE with targeted incorporations of M2 of 5, 10, 20, and 50 mol %. We have previously demonstrated that such a solvent mixture is suitable for the direct controlled (co)polymerization of cationic and betaine exo ‐7‐oxanorbornenes using the Grubbs G1 initiator . Given the limited solubility of the resulting cationic copolymers, SEC analysis in organic media, and hence, determination of the n and Đ M , was not possible.…”

“…The synthesis of functional or reactive exo ‐7‐oxanorbornenes is commonly accomplished via the imidization of exo ‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalic anhydride ( 1 ) with appropriate 1° amines . Such reactions are generally high yielding and provided 1 is used, as opposed to the exo / endo mixture, then isomerically pure functional derivatives are obtained directly that can generally be (co)polymerized in a controlled manner with G1 .…”

Combining Ring‐Opening Metathesis Polymerization and Thiol‐Ene Coupling Chemistries: Facile Access to Novel Functional Linear and Nonlinear Macromolecules

“…Somewhat surprisingly, all the shorter chain alcohol derivatives either did not polymerize or polymerized to a limited conversion with 1 but could be quantitatively polymerized with 3 . The exact reason(s) for this are unclear since 1 has been used successfully in alcoholic solvents and the direct polymerization of sugar‐norbornene monomers has been previously reported albeit under different conditions …”

Cationic Bottlebrush Polymers from Quaternary Ammonium Macromonomers by Grafting‐Through Ring‐Opening Metathesis Polymerization

“…Ligand environments around the ruthenium metal center impact metathesis activity of the catalyst. Halide ligand types can improve the initiation rate constant ( k i ) by exchanging chloride ligands for bromide or iodide ligands; however, this exchange decreases the propagation rate constant ( k p ) of the given catalyst initiator 68. Halide ligand exchange has been observed during synthesis of cationic polymers from cationic exo‐7‐norbornene derivatives using the first generation Grubbs catalyst for ROMP 68.…”

“…Halide ligand types can improve the initiation rate constant ( k i ) by exchanging chloride ligands for bromide or iodide ligands; however, this exchange decreases the propagation rate constant ( k p ) of the given catalyst initiator 68. Halide ligand exchange has been observed during synthesis of cationic polymers from cationic exo‐7‐norbornene derivatives using the first generation Grubbs catalyst for ROMP 68. Cationic monomers with bromide counter‐ions polymerized slower than their chloride counterparts, but had a narrower MWD and still followed first‐order kinetics in monomer.…”