Complex and preparation method of poly(alkylene carbonate) using the same

1. A complex represented by the following Chemical Formula 1:

in Chemical Formula 1,

M is trivalent cobalt or trivalent chromium;

A is oxygen or sulfur;

Q is a diradical connecting two nitrogens;

R 1 to R 10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus atom; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; (C6-C20)arylcarbonyl; a metalloid radical of Group 14 metal substituted with hydrocarbyl; a protonated group of the following Chemical Formula 2; a protonated group of the following Chemical Formula 3; a protonated group of the following Chemical Formula 4; a protonated group of the following Chemical Formula 5; a protonated group of the following Chemical Formula 6; a protonated group of the following Chemical Formula 7; a protonated group of the following Chemical Formula 8; or a protonated group of the following Chemical Formula 9;

wherein at least one or more of R 1 to R 10 are a protonated group selected from a group consisting of the following Chemical Formulas 2, 3, 4, 5, 6, 7, 8, and 9;

X − is halogen anion; a (C6-C20)aryloxy anion; a (C6-C20)aryloxy anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C1-C20)alkylcarboxy anion; a (C1-C20)alkylcarboxy anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C6-C20)arylcarboxy anion; a (C6-C20)arylcarboxy anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C1-C20)alkoxy anion; a (C1-C20)alkoxy anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C1-C20)alkylcarbonate anion; a (C1-C20)alkylcarbonate anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C6-C20)arylcarbonate anion; a (C6-C20)arylcarbonate anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C1-C20)alkylsulfonate anion; a (C1-C20)alkylsulfonate anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C1-C20)alkylamido anion; a (C1-C20)alkylamido anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C6-C20)arylamido anion; a (C6-C20)arylamido anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C1-C20)alkylcarbamate anion; a (C1-C20)alkylcarbamate anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C6-C20)arylcarbamate anion; or a (C6-C20)arylcarbamate anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus;

X − may be coordinated to M;

Y 1 − is F − , Cl − , Br − , I − , BF 4 − , ClO 4 − , NO 3 − or PF 6 − ;

*Y 2 2− is SO 4 2− or CO 3 2− ;

a is an integer obtained by adding 1 to the total number of monovalent cations included in protonated groups of R 1 to R 10 ;

b is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, and b+c+2d=a is satisfied;

Z 1 to Z 18 are each independently an nitrogen or phosphorus;

n is an integer of 1 to 10;

m is an integer of 1 to 10;

R 11 to R 16 , R 21 to R 26 , R 31 to R 36 , R 41 to R 48 , R 51 to R 57 , R 61 to R 66 , R 71 to R 76 and R 81 to R 86 are each independently hydrogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more selected from among halogen, nitrogen, oxygen, silicon, a 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, a 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, a sulfur and phosphorus; or a metalloid radical of Group 14 metal substituted with hydrocarbyl; two of R 11 to R 16 , two of R 21 to R 26 , two of R 31 to R 36 , two of R 41 to R 48 , two of R 51 to R 57 , two of R 61 to R 66 , two of R 71 to R 76 , and two of R 81 to R 86 may be linked with each other to thereby form a ring; and

wherein alkyl, alkenyl, alkylaryl, arylalkyl, alkoxy, aryloxy, alkylcarbonyl, and arylcarbonyl of R 1 to R 10 , and alkyl, alkenyl, alkylaryl and arylalkyl of R 11 to R 16 , R 21 to R 26 , R 31 to R 36 , R 43 to R 48 , R 51 to R 57 , R 61 to R 66 , R 71 to R 76 and R 81 to R 86 may be further substituted with any one or more selected from halogen, (C1-C20)alkyl, (C2-C20)alkenyl, (C1-C20)alkyl(C6-C20)aryl and (C6-C20)aryl(C1-C20)alkyl.

2. The complex of claim 1 , wherein Q is (C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene, (C2-C20)alkynylene or (C3-C20)cycloalkylene.

3. The complex of claim 2 , wherein

M is trivalent cobalt;

A is oxygen; and

Q is 1,2-cyclohexylene, phenylene or ethylene.

4. The complex of claim 1 , wherein at least one or more of R 1 , R 2 , R 5 and R 6 are a protonated group selected from a group consisting of Chemical Formulas 2, 3, 4, 5, 6, 7, 8, and 9 of claim 1 .

5. The complex of claim 4 , wherein R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are hydrogen.

6. The complex of claim 5 , which has a structure represented by the following Chemical Formula 11:

in Chemical Formula 11,

M is trivalent cobalt or trivalent chromium;

A is oxygen or sulfur;

R 1 and R 2 are each independently a protonated group selected from a group consisting of hydrogen, (C1-C10)alkyl, Chemical Formulas 2, 3, 4, 5, 6, 7, 8, and 9 of claim 1 ;

R 5 and R 6 identically represent hydrogen, halogen, (C1-C20)alkyl, (C2-C20)alkenyl, (C1-C20)alkoxy, (C1-C20)alkyl(C6-C20)aryl or (C6-C20)aryl(C1-C20)alkyl; alkyl, alkenyl, alkoxy, alkylaryl or arylalkyl of R 5 or R 6 may be further substituted with any one or more selected from halogen, (C1-C20)alkyl, (C2-C20)alkenyl, (C1-C20)alkoxy, (C1-C20)alkyl(C6-C20) aryl or (C6-C20)aryl(C1-C20)alkyl;

X 1 − is halogen anion; a (C1-C20)alkylcarboxy anion; a (C1-C20)alkylcarboxy anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C1-C20)alkylcarbonate anion; a (C1-C20)alkylcarbonate anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C1-C20)alkylcarbamate anion; or a (C1-C20)alkylcarbamate anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus; a (C6-C20)aryloxy anion; or a (C6-C20)aryloxy anion containing one or more selected from among halogen, nitrogen, oxygen, silicon, a sulfur and phosphorus;

X 1 − may be coordinated to Co;

Y 1 − is Cl − , Br − , BF 4 − or NO 3 − ;

Y 2 2− is SO 4 2− or CO 3 2− ;

a is an integer obtained by adding 1 to the total number of monovalent cations included in protonated groups of R 1 to R 2 ; and

b is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, and b+c+2d=a is satisfied.

7. The complex of claim 6 , which has a structure represented by any one of the following Chemical Formulas 12 to 22:

in Chemical Formulas 12 to 22,

R 2 is hydrogen or (C1-C20)alkyl;

R 5 or R 6 is hydrogen, halogen, (C1-C10)alkyl or (C1-C10)alkoxy;

R 13 , R 14 , R 23 , R 24 , R 33 , R 34 , R 41 , R 42 , R 45 , R 46 , R 53 , R 54 , R 55 , R 63 , R 66 , R 73 , R 76 , R 83 and R 86 are each independently (C1-C10)alkyl;

m or n is each independently an integer of 1 to 10;

*X − is Cl − , an acetate anion (CH 3 COO − ) or a 4-nitrophenoxy anion (NO 2 —C 6 H 5 O − );

X − may be coordinated to Co;

Y 1 − is Cl − , Br − or NO 3 − ;

Y 2 2− is SO 4 2− or CO 3 2− ; and

b is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, and b+c+2d=3 is satisfied.

8. A preparation method of poly(alkylene carbonate), comprising: copolymerizing carbon dioxide and one or more epoxide compound selected from a group consisting of (C2-C20)alkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; (C4-C20)cycloalkylene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy; and (C8-C20)styrene oxide unsubstituted or substituted with halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy or (C1-C20)alkyl in the presence of a compound represented by the following Chemical Formula 31 which is a molecular weight regulator, using the complex of claim 1 as a catalyst:

J(LH) c   [Chemical Formula 31]

in Chemical Formula 31, J is C1 to C60 hydrocarbyl c-valent radical with or without an ether group, an ester group or an amine group; LH is —OH or —CO 2 H; and c is an integer from 1 to 10, in which LH may be identical or different when c is 2 or more.

9. The preparation method of claim 8 , wherein in the compound represented by Chemical Formula 31, c is 1; and J is C1 to C60 hydrocarbyl radical with or without an ether group, an ester group, or an amine group.

10. The preparation method of claim 8 , wherein in the compound represented by Chemical Formula 31, c is 2; and J is C1 to C60 hydrocarbyl diradical with or without an ether group, an ester group, or an amine group.

11. The preparation method of claim 10 , wherein in the compound represented by Chemical Formula 31, LH is —CO 2 H; and J is —[CR 2 ] n — (n is an integer of 0 to 20; and R which may be identical or different represents hydrogen, methyl, ethyl, propyl, or butyl), para-phenylene, meta-phenylene, ortho-phenylene or 2,6-naphthalenediyl.

12. The preparation method of claim 10 , wherein in the compound represented by Chemical Formula 31, LH is —OH; and J is —[CR 2 ] n — (n is an integer of 0 to 20; and R which may be identical or different represents hydrogen, methyl, ethyl, propyl, or butyl), —CH 2 CH 2 N(R)CH 2 CH 2 — (R is C1 to C20 hydrocarbyl) or [CH 2 CH(R)O] n CH 2 CH(R)— (n is an integer of 0 to 10; and R is hydrogen or methyl).

13. The preparation method of claim 9 , wherein in the compound represented by Chemical Formula 31, LH is —OH; and J is —[CR 2 ] n — (n is an integer of 0 to 20; and R which may be identical or different represents hydrogen, methyl, ethyl, propyl, or butyl).

14. The preparation method of claim 8 , wherein in the compound represented by Chemical Formula 31, c is 3; and J is C1 to C60 hydrocarbyl triradical with or without an ether group, an ester group, or an amine group.

15. The preparation method of claim 14 , wherein in the compound represented by Chemical Formula 31, LH is —CO 2 H; and J is 1,2,3-propanetriyl, 1,2,3-benzenetriyl, 1,2,4-benzenetriyl or 1,3,5-benzenetriyl.

16. The preparation method of claim 8 , wherein in the compound represented by Chemical Formula 31, c is 4; and J is C1 to C60 hydrocarbyl tetraradical with or without an ether group, an ester group, or an amine group.

17. The preparation method of claim 16 , wherein in the compound represented by Chemical Formula 31, LH is —CO 2 H; and J is 1,2,3,4-butanetetrayl or 1,2,4,5-benzenetetrayl.