Anionic ring‐opening polymerization of a five‐membered cyclic carbonate having a glucopyranoside structure

Abstract

Anionic ring-opening polymerizations of methyl 4,6-O-benzylidene-2,3-O-carbonyl-a-D-glucopyranoside (MBCG) were investigated using various anionic polymerization initiators. Polymerizations of the cyclic carbonate readily proceeded by using highly active initiators such as n-butyllithium, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene, whereas it did not proceed by using N,N-dimethyl-4-aminopyridine and pyridine as initiators. In a polymerization of MBCG (1.0 M), 99% of MBCG was converted within 30 s to give the corresponding polymer with number-averaged molecular weight (M n ) of 16,000. However, the M n of the polymer decreased to 7500 when the polymerization time was prolonged to 24 h. It is because a backbiting reaction might occur under the polymerization conditions.

One-Pot Synthesis of Oxazolidinones and Five-Membered Cyclic Carbonates from Epoxides and Chlorosulfonyl isocyanate: Theoretical Evidence for the Asynchronous Concerted Pathway

“…Moreover, they are used as electrolyte components in Li-ion re-chargeable cells and as aprotic polar solvent with high boiling point as alternative of dangerous solvents because of their good biodegradability and low toxicity [16][17][18]. Synthetic intermediates for ring-opening polymerization of the compounds containing cyclic carbonates such as methyl 4,6-O-benzylidene-2,3-O-carbonyl-α-D-glucopyranoside (MBCG) (5) [19][20] and glycerol carbonate (6) [21] were also reported ( Figure 1). Therefore, numerous synthetic approaches have been developed to date for the preparation of oxazolidinones and five-membered cyclic carbonates in various structures.…”

Green polycarbonates prepared by the copolymerization of CO2 with epoxides

“…CO 2 fixation through reaction with the highly reactive three‐membered epoxide ring to afford cyclic or polymeric carbonates [Figure (A)] is a teeming field of research . Cyclic carbonates (CC) can find applications as green solvents with useful properties (high boiling point, high flash point, high polarity, and low vapor pressure), as electrolytes in Li‐ion batteries, and as intermediates for the synthesis of polymers and fine chemicals . Polycarbonates (PCs) represent the other interesting synthetic target of the coupling reaction between CO 2 and epoxides.…”

“…10,11 Cyclic carbonates (CC) can find applications as green solvents with useful properties (high boiling point, high flash point, high polarity, and low vapor pressure), as electrolytes in Li-ion batteries, and as intermediates for the synthesis of polymers and fine chemicals. [12][13][14][15] Polycarbonates (PCs) represent the other interesting synthetic target of the coupling reaction between CO 2 and epoxides. This review will present and discuss the synthesis, characterization, applications, and strategies for improving the properties of these green CO 2 -epoxide copolymers.…”

Synthetic Biomaterials from Metabolically Derived Synthons

“…317,318 The polymerization proceeded smoothly at room temperature and afforded sugar-derived polycarbonates in good yields (70– 98%) and without polyether moieties. However, broader Đ values (1.6–2.08) with significant formation of cyclic polymer structures due to a backbiting reaction are observed as compared to the ROP of six-membered bicyclic carbonate monomers.…”