Highly efficient enzymatic catalysis for cyclocarbonate polymerization

Abstract

In this study, we developed a metal-free biosynthetic strategy of enzymatic polymerization to fabricate aliphatic poly(pentamethylene carbonate) (PPMC). Novozym-435 lipase showed considerably high catalytic efficiency, and high molecular weights (M n ) of up to 6.0Â10 4 g mol À1 were readily achieved through the ring-opening polymerization of cyclobis(pentamethylene carbonate). The reaction parameters, including monomer concentration and lipase concentration, were examined. It seemed that little polymer degradation occurred during the polymerization, which would happen in the case of organometallic catalysis. In vitro enzymatic degradation tests indicate that the carbonate groups may not be sensitive to catalysis from the lipases of porcine pancreas and Candida rugosa (AYS). PPMC was found to possess higher flexibility and tenacity, relative to poly(trimethylene carbonate). Thermogravimetrical analyses suggest that the chemical structure of poly(alkylene carbonate)s exerts a significant influence on their thermal stability and decomposition mechanism.

Well-Defined Selenium-Containing Aliphatic Polycarbonates via Lipase-Catalyzed Ring-Opening Polymerization of Selenic Macrocyclic Carbonate Monomer

“…The ROP of M Se was investigated using the same lipase CA as the catalyst with benzyl alcohol as the initiator (Scheme ) under similar conditions as previously reported by Gross and Zhuo. , Lipase has showed the outstanding capacity for ROP of macrocyclic lactones and carbonates compared to metal and organic catalysts. , Owing to the high melting point of M Se ( T m = 93 °C, Figure S6), the ROP was carried out by solution polymerization in toluene at 70 °C. The obtained PSe structure was verified by 1 H NMR and 77 Se NMR (Figures b and S7).…”

“…33,38 Lipase has showed the outstanding capacity for ROP of macrocyclic lactones and carbonates compared to metal and organic catalysts. 35,39 Owing to the high melting point of M Se (T m = 93 °C, Figure S6), the ROP was carried out by solution polymerization in toluene at 70 °C. The obtained PSe structure was verified by 1 H NMR and 77 Se NMR (Figures 2b and S7).…”

A series of bifunctional metalloporphyrins as efficient catalysts for cycloaddition of CO2 with epoxides

“…For example, in industry, CO 2 is used as raw material to synthesize urea, 3 methanol, [4][5][6] polycarbonate, 7 and cyclic carbonate. 8,9 Among them, the 100% atom-economical cycloaddition reaction of CO 2 and epoxide to produce cyclic carbonate has the most promising development for the excellent market application value of cyclic carbonate in lithium batteries, 10 polymer materials, 11,12 fuel, 13 and other new energy fields. At present, various catalysts have been reported to have promoting effects on this cycloaddition reaction, such as quaternary ammonium salts, 14 metal complexes, 15 ionic liquids, [16][17][18][19] quaternary phosphonium salts, 20 amines, 21 metal oxides.…”

Morphosynthesis of poly[4‐(1,4‐phenylene)oxyphthalimide] and copolymers prepared by reaction‐induced crystallization during polymerization

“…Reaction-induced phase separation during isothermal polymerization has been studied to control the morphology of aromatic polymers. [10][11][12][13][14][15][16][17] The isothermal polymerization can induce phase separation from homogeneous liquid phase. The phase separation such as crystallization and liquid-liquid phase separation is determined by the miscibility between oligomers and solvents, being related to the decrease in solution mixing entropy caused by polymerization.…”