Coordination complexes for producing polycarbonate by copolymerization of carbon dioxide and epoxide using the same as catalyst
View Patent ↗Provided are a complex prepared from ammonium salt-containing ligands and having such an equilibrium structural formula that the metal center takes a negative charge of 2 or higher, and a method for preparing polycarbonate via copolymerization of an epoxide compound and carbon dioxide using the complex as a catalyst. When the complex is used as a catalyst for copolymerizing an epoxide compound and carbon dioxide, it shows high activity and high selectivity and provides high-molecular weight polycarbonate, and thus easily applicable to commercial processes. In addition, after forming polycarbonate via carbon dioxide/epoxide copolymerization using the complex as a catalyst, the catalyst may be separately recovered from the copolymer.
1. A complex represented by Chemical Formula 12:
wherein
p and q independently represent an integer from 1 to 19;
R 26 represents primary or secondary (C1-C20)alkyl;
R 27 through R 29 are independently selected from (C1-C20)alkyl and (C6-C30)aryl;
Q represents (C6-C30)arylene, (C1-C20)alkylene or (C3-C20)cycloalkylene, wherein the arylene, alkylene or cycloalkylene is optimally further substituted by a substituent selected from halogen atoms, (C1-C7)alkyl and nitro groups; and
Z 1 through Z 5 are independently selected from a halide ion; BF 4 − ; ClO 4 − ; NO 3 − ; PF 6 − ; HCO 3 − ; and a (C6-C30)aryloxy anion; (C1-C20)carboxylic acid anion; (C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion; (C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion; or (C1-C20)alkylcarbamate anion with or without at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms, wherein a part of Z 1 through Z 4 coordinated at the cobalt atom is optionally de-coordinated.
2. The complex according to claim 1 , wherein p and q independently represent an integer from 1 to 5; R 26 represents (C1-C7)alkyl; R 27 through R 29 independently represent (C1-C7)alkyl; Q represents ethylene, trans-1,2-cyclohexylene or 1,2-phenylene; Z 1 through Z 5 are independently selected from 2,4-dinitrophenolate and BF 4 − .
3. The complex according to claim 2 , wherein p and q independently represent 2; R 26 and R 27 independently represent methyl; R 28 and R 29 independently represent butyl; Q represents trans-1,2-cyclohexylene; and Z 1 through Z 5 are independently selected from 2,4-dinitrophenolate and BF 4 − .
4. A complex represented by Chemical Formula 11:
wherein
B 1 through B 4 independently represent (C3-C20)cycloalkylene;
R 26 represents primary or secondary (C1-C20)alkyl;
R 27 through R 29 are independently selected from (C1-C20)alkyl and (C6-C 30 )aryl;
Q represents divalent bridge group for linking the two nitrogen atoms; and
Z 1 through Z 5 are independently selected from a halide ion; BF 4 − ; ClO 4 − ; NO 3 − ; PF 6 − ; HCO 3 − ; and a (C6-C30)aryloxy anion; (C1-C20)carboxylic acid anion; (C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion; (C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion; (C1-C20)alkycarbamate anion or anion of Meisenheimer slat with or without at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms, wherein a part of Z 1 through Z 4 coordinated at the cobalt atom is optionally de-coordinated.