Catalytic system of nitrate anions for CO2/epoxide copolymerization

A method of preparing polycarbonate, comprising:

• copolymerizing carbon dioxide and one or more epoxide compounds selected from the group consisting of (C2-C20)alkylene oxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyloxy;
• (C4-C20)cycloalkylene oxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyloxy;
• and (C8-C20)styrene oxide substituted or unsubstituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyloxy or (C1-C20)alkyl using a complex compound of Formula 3 below as a catalyst, thus preparing polycarbonate;
• and
• bringing a solution in which the prepared copolymer and the catalyst are dissolved into contact with a solid inorganic material, a polymer material or a mixture thereof insoluble in the solution, thus forming a composite of solid inorganic material or polymer material and catalyst, thereby separating the copolymer and the catalyst from each other:
• In Formula 3, M is trivalent cobalt or trivalent chromium;
• A is oxygen or sulfur;
• Q is a diradical that connects two nitrogen atoms;
• R1 to R10 are each independently hydrogen;
• halogen;
• (C1-C20)alkyl;
• (C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C2-C20)alkenyl;
• (C2-C20)alkenyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C1-C20)alkyl(C6-C20)aryl;
• (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C6-C20)aryl(C1-C20)alkyl;
• (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C1-C20)alkoxy;
• (C6-C30)aryloxy;
• formyl;
• (C1-C20)alkylcarbonyl;
• (C6-C20)arylcarbonyl;
• or a metalloid radical of Group 14 metal substituted with hydrocarbyl;
• two of R1 to R10 may be linked with each other to form a ring;
• at least one of R3 to R10 is a proton group selected from among Formula a, Formula b and Formula c as represented below:
• Z is nitrogen or phosphorus;
• R11, R12, R13, R21, R22, R23, R24 and R25 are each independently (C1-C20)alkyl;
• (C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C2-C20)alkenyl;
• (C2-C20)alkenyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C1-C20)alkyl(C6-C20)aryl;
• (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C6-C20)aryl(C1-C20)alkyl;
• (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• or a metalloid radical of Group 14 metal substituted with hydrocarbyl;
• two of R11, R12 and R13 or two of R21, R22, R23, R24and R25 may be linked with each other to form a ring;
• R31, R32 and R33 are each independently hydrogen;
• (C1-C20)alkyl;
• (C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C2-C20)alkenyl;
• (C2-C20)alkenyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C1-C20)alkyl(C6-C20)aryl;
• (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C6-C20)aryl(C1-C20)alkyl;
• (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• or a metalloid radical of Group 14 metal substituted with hydrocarbyl;
• two of R31, R32 and R33 may be linked with each other to form a ring;
• X′ is oxygen, sulfur or N—R (wherein R is (C1-C20)alkyl);
• a is a number obtained by adding 1 to the number of proton groups included in R3 to R10;
• b is an integer of 1 or more;
• and
• a nitrate or acetate anion may be coordinated to M.

A method of separating and recovering a catalyst and a catalyst precursor from a solution in which a copolymer and the catalyst are dissolved, comprising:

• copolymerizing carbon dioxide and one or more epoxide compounds selected from the group consisting of (C2-C20)alkylene oxide substituted or unsubstituted with halogen or (C1-C20)alkoxy;
• (C4-C20)cycloalkylene oxide substituted or unsubstituted with halogen or (C1-C20)alkoxy;
• and (C8-C20)styrene oxide substituted or unsubstituted with halogen, (C1-C20)alkoxy or (C1-C20)alkyl using a complex compound of Formula 3 below as a catalyst, thus preparing polycarbonate;
• bringing a solution in which the prepared copolymer and the catalyst are dissolved into contact with a solid inorganic material, a polymer material or a mixture thereof insoluble in the solution, thus forming a composite of solid inorganic material or polymer material and catalyst, thereby separating the copolymer and the catalyst from each other;
• and
• treating the composite of solid inorganic material or polymer material and catalyst with nitric acid or nitrate salt in a medium which does not dissolve the composite of solid inorganic material or polymer material and catalyst, thus dissolving out the catalyst or the catalyst precursor from the medium, thereby separating and recovering the catalyst and the catalyst precursor:
• In Formula 3, M is trivalent cobalt or trivalent chromium;
• A is oxygen or sulfur;
• Q is a diradical that connects two nitrogen atoms;
• R1 to R10 are each independently hydrogen;
• halogen;
• (C1-C20)alkyl;
• (C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C2-C20)alkenyl;
• (C2-C20)alkenyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C1-C20)alkyl(C6-C20)aryl;
• (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C6-C20)aryl(C1-C20)alkyl;
• (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C1-C20)alkoxy;
• (C6-C30)aryloxy;
• formyl;
• (C1-C20)alkylcarbonyl;
• (C6-C20)arylcarbonyl;
• or a metalloid radical of Group 14 metal substituted with hydrocarbyl;
• two of R1 to R10 may be linked with each other to form a ring;
• at least one of R3 to R10 is a proton group selected from among Formula a, Formula b and Formula c as represented below:
• Z is nitrogen or phosphorus;
• R11, R12, R13, R21, R22, R23, R24 and R25 are each independently (C1-C20)alkyl;
• (C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C2-C20)alkenyl;
• (C2-C20)alkenyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C1-C20)alkyl(C6-C20)aryl;
• (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C6-C20)aryl(C1-C20)alkyl;
• (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• or a metalloid radical of Group 14 metal substituted with hydrocarbyl;
• two of R11, R12 and R13 or two of R21, R22, R23, R24 and R25 may be linked with each other to form a ring;
• R31, R32 and R33 are each independently hydrogen;
• (C1-C20)alkyl;
• (C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C2-C20)alkenyl;
• (C2-C20)alkenyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C1-C20)alkyl(C6-C20)aryl;
• (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• (C6-C20)aryl(C1-C20)alkyl;
• (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, sulfur and phosphorus;
• or a metalloid radical of Group 14 metal substituted with hydrocarbyl;
• two of R31, R32 and R33 may be linked with each other to form a ring;
• X′ is oxygen, sulfur or N—R (wherein R is (C1-C20)alkyl);
• a is a number obtained by adding 1 to the number of proton groups included in R3 to R10;
• b is an integer of 1 or more;
• and
• a nitrate or acetate anion may be coordinated to M.