Copolymerization of Epichlorohydrin and CO₂ Using Zinc Glutarate: An Additional Application of ZnGA in Polycarbonate Synthesis

Abstract

The use of zinc glutarate (ZnGA) as a heterogeneous catalyst for the copolymerization of epichlorohydrin, an epoxide with an electron-withdrawing substituent, and CO2 is reported. This catalyst shows the highest selectivity (98%) for polycarbonate over the cyclic carbonate in epichlorohydrin/CO2 copolymerization under mild conditions. The (epichlorohydrin-co-CO2 ) polymer exhibits a high glass transition temperature (Tg ), 44 °C, which is the maximum Tg value obtained for the (epichlorohydrin-co-CO2 ) polymer to date.

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO2 using Zinc Glutarate Catalyst

“…Potent catalysts comprise metal complexes (Co, Cr, Zn) with macrocyclic porphyrin, [19][20][21][22][23][24] salen [25][26][27][28][29][30][31][32][33][34][35][36][37][38] or β-diiminate-type ligands [39][40][41][42][43][44][45] or heterogeneous compounds, such as ternary rare-earth metal/zinc-dialkyl mixtures, [46][47][48][49] double metal cyanide complexes (DMC) [50][51][52][53][54][55][56][57][58] and zinc dicarboxylates. [59][60][61][62][63][64][65][66][67] Control over the molecular weight may be desirable, e. g. for use in water-based dispersions…”

A Rational Investigation of the Lewis Acid-Promoted Coupling of Carbon Dioxide with Cyclohexene Oxide: Towards CO2-Sourced Polycyclohexene Carbonate under Solvent- and Cocatalyst-Free Conditions

“…Thus, for the selective and efficient synthesis of polycarbonates (PCs) from the copolymerization of CO 2 and epoxides, many Lewis acid catalysts such as organometallic complexes usually used in combination with a nucleophile have been developed. In particular, the important characteristics of metal-based catalysts (zinc [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37], aluminum [38,39], chromium [40][41][42][43], cobalt [44][45][46][47], magnesium [48,49], iron [19,[50][51][52][53][54], titanium [55,56], copper [57], ytterbium [58], . .…”

A Zn-MOF-Catalyzed Terpolymerization of Propylene Oxide, CO2, and β-butyrolactone

“…The conversion of CO 2 into chemical commodities, particularly the synthesis of biodegradable poly(alkylene carbonates) by the alternating copolymerization of an epoxide and CO 2 , is regarded as one of the most sustainable approaches for the use of CO 2 as a source material in large-scale industrial processes [1][2][3][4][5][6][7][8][9][10][11]. Poly(alkylene carbonates) are characterized by a variety of properties, e.g., lightness, strength, durability, high transparency, heat resistance, and good electrical insulating ability.…”

“…The copolymerization of epoxides and CO 2 was first reported by Tsuruta and Inoue [2,3] in 1969, since when a variety of homogeneous and heterogeneous catalysts have been developed for the copolymerization of CO 2 and epoxides [7,[14][15][16][17][18][19][20][21][22][23][24][25]. Among these catalysts, zinc glutarate (ZnGA) has been widely employed as a heterogeneous catalyst in industry because it is economical and nontoxic, can be easily synthesized and dealt with, and affords high-molecular-weight copolymers [7,11,21,24,25].…”

“…More recently, Rieger et al [56] reported the homogeneous zinc-catalyzed one-pot synthesis of AB, ABA block terpolymers from BBL, cyclohexene oxide (CHO), and CO 2 , where the selectivity could be tuned by CO 2 .From this background, the terpolymerization of PO, BBL, and CO 2 still remains to be achieved. Herein, as part of our continued research efforts to improve the catalytic activity of ZnGA and explore additional applications for ZnGA [11], we report the ZnGA-catalyzed terpolymerization of PO, BBL, and CO 2 (Scheme 1), which affords poly(ester-co-carbonates) with thermal and mechanical properties that can be tuned by adjusting the ratio of PO to BBL in the feedstock.…”