Facile synthesis of poly(ether carbonate)s via copolymerization of CO₂and propylene oxide under combinatorial catalyst of rare earth ternary complex and double metal cyanide complex

Abstract

Poly(ether carbonate)s (PPCs) with carbonate unit (CU) content ranging from 57.8 to 97.1% and number average molecular weight (Mn) around 100 kg/mol were conveniently prepared via copolymerization of CO2 and propylene oxide under combinatorial catalyst of rare earth ternary (RET) complex and double metal cyanide (DMC) complex. Enhancement of catalytic activity and reduction of propylene carbonate byproduct were realized due to synergetic effect of the two metal catalysts, where DMC can be activated in the presence of RET. Solubility fractionation confirmed that the obtained PPCs were copolymers, not physical blends of each polymer. Thermal performances of the PPCs were closely related to their CU content, their glass transition temperatures (Tg) were tunable in the range of 6.7–36.3 °C, which decreased with decreasing CU content, while their thermal stabilities were enhanced significantly, an increase of 50.5 °C in 50% weight loss temperature was observed when CU content decreased from 97.1 to 57.8%. Both shear storage modulus and complex viscosity increased with increasing CU content, which became more obvious at lower frequency, featuring well with the CU content in the PPCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Synthesis of Zn–Fe double metal cyanide complexes with imidazolium-based ionic liquid cocatalysts via ball milling for copolymerization of CO2 and propylene oxide

“…[8][9][10][11] It is generally accepted that effective catalysts are critical for the successful synthesis of propylene carbonates from CO 2 and epoxides. Since the initial discovery by Inoue and coworkers of the ZnEt 2 and water catalyst for the reaction of CO 2 and epoxides, 12,13 researchers have developed a wide variety of catalytic systems for the synthesis of polycarbonates including zinc carboxylates, 14 Salen metal compounds, 15 b-diiminate zinc derivatives, 16 organic bases, 17 metalloporphyrins, 18 a rare-earth ternary catalyst, 19 organic ammonium halogenides and others. [20][21][22][23] Among these, double metal cyanide (DMC) catalysts display excellent catalytic activity for the copolymerization of CO 2 and epoxides via several different reaction mechanisms.…”

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

“…Both heterogeneous and homogeneous catalysts are known, with the latter generally showing significantly faster rates and much finer control compared to the solid-state materials. This review only briefly describes heterogeneous or surface catalysis; for more insights into this topic, the reader is referred to previous reports and reviews [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32]. It is also important to draw the reader's attention to various comprehensive reviews in the area of homogeneous catalysis [6,[33][34][35][36][37][38][39][40][41][42][43][44][45][46].…”

Recent advances in carbon dioxide based copolymers

“…Typical heterogeneous catalysts include ZnEt 2 -active hydrogen containing compound systems [11][12][13], zinc dicarboxylates [14][15][16][17][18], double metal cyanide complexes [19][20][21][22][23][24][25][26], and rare-earth metal coordination ternary catalysts [27][28][29][30][31], though the chemical structures or crystal structures of heterogeneous catalysts are not clear, they are convenient in synthesis and handling, showing more potentiality for industrial purpose.…”