Method for preparing carbon dioxide/epoxide copolymers containing ether linkages

1. A method for preparing poly(alkylene carbonate) containing ether linkages, by the copolymerization of an epoxide compound and carbon dioxide, with a complex of Chemical Compound I below and a double metal cyanide (DMC) catalyst together,

wherein, in Chemical Formula 1,

M represents trivalent cobalt or trivalent chromium;

A represents an oxygen or sulfur atom;

Q represents a diradical linking two nitrogen atoms;

R 1 through R 10 each independently represents hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; (C6-C20)arylcarbonyl; or a metalloid radical of group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl;

two of R 1 through R 10 may be linked to each other to form a ring;

at least one of hydrogens included in R 1 through R 10 and Q is substituted with a cationic group selected from the group consisting of Chemical Formula a, Chemical Formula b, and Chemical Formula c below;

X − each independently represents a halide anion; HCO 3 − ; BF 4 − ; ClO 4 − ; NO 3 − ; PF 6 − ; (C6-C20)aryloxy anion; (C6-C20)aryloxy anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20)alkylcarboxyl anion; (C1-C20)alkyl carboxyl anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C6-C20)arylcarboxyl anion; (C6-C20)arylcarboxyl anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20)alkoxy anion; (C1-C20)alkoxy anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20)alkylcarbonate anion; (C1-C20)alkylcarbonate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C6-C20)arylcarbonate anion; (C6-C20)arylcarbonate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20)alkylsulfonate anion; (C1-C20)alkylsulfonate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20)alkylamido anion; (C1-C20)alkylamido anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C6-C20)arylamido anion; (C6-C20)arylamido anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20)alkylcarbamate anion; (C1-C20)alkylcarbamate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; or (C6-C20)arylcarbamate anion; (C6-C20)arylcarbamate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;

Z represents a nitrogen or phosphorus atom;

R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represents (C1-C20)alkyl; (C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; or a metalloid radical of group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl; and two of R 21 , R 22 and R 23 , or two of R 31 , R 32 , R 33 , R 34 and R 35 may be linked to each other to form a ring;

R 41 , R 42 and R 43 each independently represents hydrogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; or a metalloid radical of group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl; and two of R 41 , R 42 and R 43 may be linked to each other to form a ring;

X′ represents an oxygen atom, a sulfur atom, or N—R (here, R represents (C1-C20)alkyl);

n represents an integer obtained by adding 1 to the total number of cationic groups contained in R 1 to R 10 and Q;

X − may be coordinated to M; and

a nitrogen atom of imine may be coordinated to M or may be decoordinated from M.

2. The method of claim 1 , wherein the epoxide compound is at least one compound selected from the group consisting of (C2-C20)alkyleneoxide substituted or unsubstituted with halogen, (C1-C20)alkoxy, (C6-C20)aryloxy, or (C6-C20)ar(C1-C20)alkoxy; (C4-C20)cycloalkyleneoxide substituted or unsubstituted with halogen, (C1-C20)alkoxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkoxy; and (C8-C20)styreneoxide substituted or unsubstituted with halogen, (C1-C20)alkoxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkoxy, or (C1-C20)alkyl.

3. The method of claim 1 , wherein in Chemical Formula 1, M represents trivalent cobalt; A represents an oxygen atom; Q represents trans-1,2-cyclohexylene, phenylene, or ethylene; R 1 and R 2 represent the same or different primary (C1-C20)alkyl; R 3 through R 10 each independently represents hydrogen or —[YR 51 3-a {(CR 52 R 53 ) b N + R 54 R 55 R 56 } a ]; Y represents C or Si; R 51 , R 52 , R 53 , R 54 , R 55 and R 56 each independently represents hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; (C6-C20)arylcarbonyl; or a metalloid radical of group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl, and two of R 54 , R 55 and R 56 may be linked to each other to form a ring; a represents an integer of 1 to 3; b represents an integer of 1 to 20; n represents an integer of 4 or more, which is obtained by adding 1 to the total number of quaternary ammonium salts contained in R 3 through R 10 ; provided that, at least three of R 3 through R 10 represent —[YR 51 3-a {(CR 52 R 53 ) b N + R 54 R 55 R 56 } a ] when a represents 1, at least two of R 3 through R 10 represent —[YR 51 3-a {(CR 52 R 53 ) b N + R 54 R 55 R 56 } a ] when a represents 2, and at least one of R 3 through R 10 represents —[YR 51 3-a {(CR 52 R 53 ) b N + R 54 R 55 R 56 } a ] when a represents 3.

4. The method of claim 1 , wherein the compound of Chemical Formula 1 is a complex represented by Chemical Formula 2 below, the double metal cyanide (DMC) catalyst is a complex represented by Chemical Formula 3,

wherein, in Chemical Formula 2, R 61 and R 62 each independently represents methyl or ethyl; X − each independently represents a nitrate or acetate anion; the nitrogen of imine may be coordinated to cobalt or may be decoordinated from cobalt, and respective anions may be coordinated to cobalt,

Zn 3 [Co(ON) 6 ] 2 .x ZnCl 2 .y H 2 O. z A  [Chemical Formula 3]

wherein, in Chemical Formula 3, A represents a hydrocarbon including alcohol, aldehyde, ketone, ether, ester, amide, nitrile, or sulfide group; x represents a rational number of 0.001 to 3.0; y represents a rational number of 0.1 to 10; and z represents a rational number of 0.01 to 10.

5. The method of claim 4 , wherein in the complex of Chemical Formula 3, A represents tert-butyl alcohol.

6. The method of claim 4 , wherein the epoxide compound is propylene oxide or ethylene oxide.

7. The method of claim 1 , wherein the complex of Chemical Formula 1 and the double metal cyanide (DMC) catalyst are used at a weight ratio of 95:5 to 5:95.

8. The method of claim 7 , wherein the complex of Chemical Formula 1 and the double metal cyanide (DMC) catalyst are used at a weight ratio of 3:7 to 7:3.