Highly Selective Synthesis of CO₂ Copolymer from Styrene Oxide

Carbon Dioxide/Epoxide Copolymerization via a Nanosized Zinc–Cobalt(III) Double Metal Cyanide Complex: Substituent Effects of Epoxides on Polycarbonate Selectivity, Regioselectivity and Glass Transition Temperatures

“…It is of great interest to investigate the regiochemistry of the CO 2 /epoxide copolymerization because regioregular CO 2 /epoxide copolymers should expand the range of the thermal and mechanical properties of the resulting copolymers versus their regioirregular counterparts. 10,13,15,45,48 Here, CO 2 /epoxide copolymers with highly alternating degrees (94.2% ->99%, entries 4−11 in Table 1) were selected for further analysis of regiochemistry because the carbonate anion (−OOCO − ) was the main nucleophilic species attacking the methylene (CH 2 ) or methine (CH) sites to open the epoxide ring (Scheme 2). CO 2 /J copolymerization was highly regioselective under Zn− Co(III) DMCC catalysis 14 and afforded a CO 2 /J copolymer with 90% HT connectivity (50°C).…”

“…Lu and Daresnbourget al 13 reported a perfect alternating CO 2 / styrene oxide (SO) copolymerization using a (Salen)Co(III) complex anchoring 1,5,7-triabiabicyclo [4,4,0]dec-5-ene and (Salen)Cr(III)/(PPN)Cl at 25°C, which afforded a fully alternating poly(styrene carbonate) (PSC). Recently, our group reported an alternating and regioregular PSC with an alternating degree of 99.4% and 96% head-to-tail (HT) connectivity using nanosized zinc−cobalt(III) double metal cyanide complex [Zn−Co(III)DMCC] catalysts without introducing any cocatalysts or catalyst promoters.…”

“…13 C NMR spectrum (125 MHz, CDCl 3 ) of poly(isobutene oxide) from CO 2 /G copolymerization with Zn−Co(III) DMCC. Key: TT = tailto-tail; HT = head-to-head; HH = head-to-head.…”

What's new with CO2? Recent advances in its copolymerization with oxiranes

“…This method of operation is consistent with the immortal nature of the polymerizations noted for these systems as well as the low conversion to cyclic carbonate byproducts observed for each case. [20][21][22] In summary, salen ligands bearing appended bulky amines or quaternary ammonium salts have several advantages over their simple counterparts:…”

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

“…30) [15,38,99]. The catalyst with an anchored TBD group, 20a, was highly active (TOF up to 10,000 h À1 ) and selective (>97%), even at high temperatures (up to 100 C), for CHO/CO 2 and PO/CO 2 copolymerisations [172,176] as well as for SO/CO 2 copolymerisation [177]. In addition, the catalyst afforded epichlorohydrin/CO 2 copolymers (>99% carbonate linkages).…”