Ring-opening copolymerization of cyclic epoxide and anhydride using a five-coordinate chromium complex with a sterically demanding amino triphenolate ligand

Abstract

This work describes polyester synthesis via alternating ring-opening copolymerization of epoxides and anhydrides using a trigonal bipyramidal chromium complex containing a sterically demanding ligand.

Record Productivity and Unprecedented Molecular Weight for Ring‐Opening Copolymerization of Epoxides and Cyclic Anhydrides Enabled by Organoboron Catalysts

“…Table 2 summarizes some key research milestones that were reached in the last 10 years. As shown, the highest molecular weights ( M n =43.8 kDa, Ð =1.21) of poly(CHO‐ alt ‐PA)s were produced in the presence of triphenolate Cr/DMAP (4‐dimethylaminopyridine) as reported by Son (Table 2 entry 17) [16] . Contrastively, in our work, an average molecular weight of over 90.0 kDa was produced at a condition of CHO/PA/ 4 =1000:1000:1 (Table 1 entry 11; Table 2 entry 3).…”

“…To comprehensively quantify the catalyst activity and evaluate the performance of our catalyst, we employed the commonly used criteria (including TOF, TON, catalytic efficiency, the highest molecular weight, and the highest working temperature) to compare with the state‐of‐the‐art organic catalysts (PPNCl, [12] BEt 3 /PPNCl, [13] and Urea/PPNCl [10f] ) and metallic compounds (porphyrinato Cr/DMAP, [7a] heterodinuclear Zn‐Mg, [17] salophen Cr/DMAP, [15] Zn(C 6 F 5 ) 2 /DMAP, [4g] and triphenolate Cr/DMAP [16] ).…”

Record Productivity and Unprecedented Molecular Weight for Ring‐Opening Copolymerization of Epoxides and Cyclic Anhydrides Enabled by Organoboron Catalysts

“…To comprehensively quantify the catalyst activity and evaluate the performance of our catalyst, we employed the commonly used criteria (including TOF, TON, catalytic efficiency,t he highest molecular weight, and the highest working temperature) to compare with the state-of-the-art organic catalysts (PPNCl, [12] BEt 3 /PPNCl, [13] and Urea/ PPNCl [10f] )and metallic compounds (porphyrinato Cr/DMA-P, [7a] heterodinuclear Zn-Mg, [17] salophen Cr/DMAP, [15] Zn-(C 6 F 5 ) 2 /DMAP, [4g] and triphenolate Cr/DMAP [16] ).…”

Heterodinuclear catalysts Zn(ii)/M and Mg(ii)/M, where M = Na(i), Ca(ii) or Cd(ii), for phthalic anhydride/cyclohexene oxide ring opening copolymerisation

“…5,15,[24][25][26][27][28] Amongst the leading PA/CHO ROCOP catalysts are bicomponent metal catalyst + ionic co-catalyst systems (PPNCl), commonly featuring Al(III), Co(III) or Cr(III) coordinated by salen, salophen, triphenolate or porphyrin ligands. 25,[29][30][31][32] For example, one of the more active systems is Cr(III)-salen/PPNCl, which showed a turn-over-frequency (TOF) of approx. 60 h −1 (k obs = 12.0 × 10…”