Controlled Anionic Polymerization of tert-Butyl Acrylate with Diphenylmethylpotassium in the Presence of Triethylborane

High Efficiency Organic Lewis Pair Catalyst for Ring-Opening Polymerization of Epoxides with Chemoselectivity

“…Organoboranes are typical Lewis acids that have been used in ionic polymerizations as initiators, monomer activators, and/or chain-end coordinators. − Unlike alkylaluminum, which is prone to undergoing side reactions such as hydride transfer, , organoboranes are reasonably stable in polymerization systems. It shows that strongly Lewis acidic tris­(perfluorophenyl)­borane readily triggers (but poorly controls) ROP of epoxides at RT with or without hydroxy compounds, − while less acidic triphenylborane (Ph 3 B) and triethylborane (Et 3 B) are ineffective at all when used alone. , Here, we use the combination of organobases with relatively low basicity (e.g., t -BuP 1 ) and Et 3 B to catalyze hydroxyl-initiated ROP of epoxides.…”

Updates in the War Against Terrorism

“…Thus, the low concentration of the active chain ends in the living radical polymerizations also greatly reduces intermolecular deactivation reactions and is an essential element in conferring living character to this polymerization 3. There are several other recent reports on the living anionic polymerization of (meth)acrylates in which dormant species are postulated or demonstrated 4–6. The situation is quite similar in some cationic polymerizations in which several species with widely different reactivities have been demonstrated 7…”

Anionic polymerization of MMA initiated by organolithium/cuprum diphenylphosphide (Ph2PCu) and synthesis of its block copolymer

“…[16][17][18] In addition to GTP and MFA, classical anionic polymerization can also show living characteristics with ligands capable of coordinating with enolate ion pairs. [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] However, the use of ligands has several disadvantages, such as high cost, complex initiator composition, and severe reaction conditions.…”

“…The breakthroughs achieved thus far include group transfer polymerization (GTP) of silyl ketene acetal and metal‐free anionic polymerization (MFA), which were developed in the 1980s 16–18. In addition to GTP and MFA, classical anionic polymerization can also show living characteristics with ligands capable of coordinating with enolate ion pairs 19–34. However, the use of ligands has several disadvantages, such as high cost, complex initiator composition, and severe reaction conditions.…”