Catalytic System for CO2/Epoxide Copolymerization

摘要

The present invention relates to a method of manufacturing a polycarbonate including the process of copolymerizing epoxide compound and CO2 using cobalt(III) or chromium(III), where the ligands contains at least 3 ammonium cations, central metal has formal −1 charge, and conjugated anions of the two cationic ammonium groups are acid-base homoconjugation, as catalyst. According to the present invention, the initial induction time can be reduced when the polycarbonate is manufactured and it is possible to improve the activity of the catalyst and the molecular weight of the obtained polymer.

主权项

1. A method of manufacturing a complex of following formula 1 (said L1, L2, and X are same as those of following formula 1), comprising:
a step of reacting a ligand of L1 or L2 with metal acetate (the metal is cobalt or chromium) to bind the metal with ligand; and a step of adding the acid (HX) in the presence of oxygen after binding said metal with ligand, and oxidizing the metal to coordinate anion X to the metal; and a step of ion exchanging by using the metal salt (the metal is lithium, sodium, potassium) having anion X:
[L1L2L3L4M]−[X1 . . . H . . . X2]−aZ−b  [formula 1] where, M is cobalt(III) or chromium(III); L1 to L4 are anionic X-type ligands, L1 to L4 are same or, different respectively, also is able to form bidentate, tridentate or tetradentate by linking each other, at least one of L1 to L4 include quaternary ammonium salt, the number of total ammonium cation included in L1 to L4 is 1+a+b, and hence the complex is overall neutral; a or b is an integer; the ligand(s) among L1 to L4 except the ligand including the quaternary ammonium cation, or X1 and X2 are each: other independently halogen anion or HCO3−, or aryloxy anion having carbon number 6 to 20 including or non-including one or more of halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphor atom, carboxy anion having carbon number 1 to 20; alkoxy anion having carbon number 1 to 20; carbonate anion having carbon number 1 to 20; alkylsulfonate anion having carbon number 1 to 20; amide anion having carbon number 1 to 20; carboxamide anion having carbon number 1 to 20; sulfonamide anion having carbon number 1 to 20; or carbamate anion having carbon number 1 to 20, Z is BF4−, ClO4−, NO3− or PF6−.