Preparation of High-Molecular-Weight Aliphatic Polycarbonates by Condensation Polymerization of Diols and Dimethyl Carbonate

Abstract

Cyclohexane-1,4-dimethanol/DMC Condensation Polymerization. The first step was conducted with cyclohexane-1,4-dimethanol (10.0 g, 69 mmol, a mixture of cisand transisomers in 3:7 ratio), NaH (3.3 mg, 0.14 mmol) and DMC (10.3 g, 114 mmol), using identical conditions and procedures to those used for DB/DMC condensation polymerization. In the second step, the condensation reaction was conducted at 180 °C and 380 mmHg for 1 h, at 210 °C and 0.3 mmHg for 1 h, and finally at 240 °C and 0.3 mmHg for 3 h. The catalyst was neutralized with phthaloyl dichloride using the same procedures and conditions as those used for DB/DMC condensation polymerization. 1 H NMR (CDCl 3 ):  4.04 (d, J = 7.2 Hz, 1.2H, 2 CH 2 OC(O) in cis-isomer), 3.94 (d, J = 6.4 Hz, 2.8H, CH 2 OC(O) in trans-isomer), 2.10-0.80 (m, 10H) ppm.

One-pot synthesis of high-molecular-weight aliphatic polycarbonates via melt transesterification of diphenyl carbonate and diols using Zn(OAc)2 as a catalyst

“…The morphology of the catalysts was investigated by means of a scanning electron microscope (Inspect F, FEI/Holland). Additionally, some typical catalysts including CH 3 ONa [3,18], NaOH [30]and TiO 2 /SiO 2 (PVP) [5,6] also gave rather poor catalytic performance in this system under identical conditions, though they have been reported to be excellent catalysts in condensation polymerization of DMC and diols in two-step process. Table 1 shows the catalytic activities of different transition metal acetates for the melt transesterification of DPC and BD at given conditions.…”

Aliphatic–aromatic poly(butylene carbonate‐co‐terephthalate) random copolymers: Synthesis, cocrystallization, and composition‐dependent properties

“…[1][2][3][4][5][6][7][8][9][10][11][12][13] Compared with aliphatic polyesters, APCs are more feasible candidates for biomedical applications, owing to the absence of acidic compounds during the in vivo degradation. 19 DMC is renowned because it can be easily handled and is cheap, nontoxic, and high biodegradability, which make them true green materials. [14][15][16][17][18] The best method to obtain APCs in which the carbonate linkages are connected by more than three carbon atoms is the condensation polymerization of dimethyl carbonate (DMC) and aliphatic diols.…”

“…APCs can be prepared by copolymerization of CO 2 and epoxides or ring-opening polymerization method. [19][20][21][22] Among the resulting APCs, poly(butylene carbonate) (PBC) has attracted most interest because of its favorable comprehensive properties and competitive cost. 19 DMC is renowned because it can be easily handled and is cheap, nontoxic, and high biodegradability, which make them true green materials.…”

Environmentally-Benign Dimethyl Carbonate-Mediated Production of Chemicals and Biofuels from Renewable Bio-Oil

“…Various catalysts, such as Sn compounds, calcined MgAl hydrotalcites, Ca, a TiO 2 /SiO 2 complex system, and sodium alkoxide, have been used in the condensation polymerization of various diols with DMC to produce aliphatic polycarbonates [71][72][73][74][75]. Aliphatic polycarbonates are attractive materials due to their favorable biodegradability, biocompatibility, and non-toxic characteristics [74,75]. López-Garzón et al [76] developed a green upgrading process for dimethyl succinate production by using DMC as a solvent and an alkylating agent catalyzed by a strong anion exchange resin.…”