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

Abstract

The present invention is directed to a novel complex synthesized from a Salen-type ligand. The novel complex contains a quaternary ammonium salt. The present invention is also directed to a preparation method of a copolymer of carbon dioxide and epoxide using the complex synthesized from a Salen-type ligand as a catalyst.

Claims

1. A complex represented by the following Chemical Formula 1: ##STR00027## in Chemical Formula 1, M is trivalent cobalt or trivalent chromium; A is oxygen or sulfur; Q is a diradical connecting two nitrogens; R.sup.1 to R.sup.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.sup.1 to R.sup.10 are a protonated group selected from a group consisting of the following Chemical Formulas 2, 3, 4, 5, 6, 7, 8, and 9; ##STR00028## X.sup.− 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.sup.− may be coordinated to M; Y.sub.1.sup.− is F.sup.−, Cl.sup.−, Br.sup.−, I.sup.−, BF.sub.4.sup.−, ClO.sub.4.sup.−, NO.sub.3.sup.− or PF.sub.6.sup.−; *Y.sub.2.sup.2− is SO.sub.4.sup.2− or CO.sub.3.sup.2−; a is an integer obtained by adding 1 to the total number of monovalent cations included in protonated groups of R.sup.1 to R.sup.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.sub.1 to Z.sub.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.sup.11 to R.sup.16, R.sup.21 to R.sup.26, R.sup.31 to R.sup.36, R.sup.41 to R.sup.48 , R.sup.51 to R.sup.57, R.sup.61 to R.sup.66, R.sup.71 to R.sup.76 and R.sup.81 to R.sup.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.sup.11 to R.sup.16, two of R.sup.21 to R.sup.26, two of R.sup.31 to R.sup.36, two of R.sup.41 to R.sup.48, two of R.sup.51 to R.sup.57, two of R.sup.61 to R.sup.66, two of R.sup.71 to R.sup.76, and two of R.sup.81 to R.sup.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.sup.1 to R.sup.10, and alkyl, alkenyl, alkylaryl and arylalkyl of R.sup.11 to R.sup.16, R.sup.21 to R.sup.26, R.sup.31 to R.sup.36, R.sup.43 to R.sup.48, R.sup.51 to R.sup.57, R.sup.61 to R.sup.66, R.sup.71 to R.sup.76 and R.sup.81 to R.sup.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.sup.1, R.sup.2, R.sup.5 and R.sup.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.sup.3, R.sup.4, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are hydrogen.

6. The complex of claim 5, which has a structure represented by the following Chemical Formula 11: ##STR00029## in Chemical Formula 11, M is trivalent cobalt or trivalent chromium; A is oxygen or sulfur; R.sup.1 and R.sup.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.sup.5 and R.sup.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.sup.5 or R.sup.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.sub.1.sup.− 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.sub.1.sup.− may be coordinated to Co; Y.sub.1.sup.− is Cl.sup.−, Br.sup.−, BF.sub.4.sup.− or NO.sub.3.sup.−; Y.sub.2.sup.2− is SO.sub.4.sup.2− or CO.sub.3.sup.2−; a is an integer obtained by adding 1 to the total number of monovalent cations included in protonated groups of R.sup.1 to R.sup.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: ##STR00030## ##STR00031## ##STR00032## in Chemical Formulas 12 to 22, R.sup.2 is hydrogen or (C1-C20)alkyl; R.sup.5 or R.sup.6 is hydrogen, halogen, (C1-C10)alkyl or (C1-C10)alkoxy; R.sup.13, R.sup.14, R.sup.23, R.sup.24, R.sup.33, R.sup.34, R.sup.41, R.sup.42, R.sup.45, R.sup.46, R.sup.53, R.sup.54, R.sup.55, R.sup.63, R.sup.66, R.sup.73, R.sup.76, R.sup.83 and R.sup.86 are each independently (C1-C10)alkyl; m or n is each independently an integer of 1 to 10; *X.sup.− is Cl.sup.−, an acetate anion (CH.sub.3COO.sup.−) or a 4-nitrophenoxy anion (NO.sub.2—C.sub.6H.sub.5O.sup.−); X.sup.− may be coordinated to Co; Y.sub.1.sup.− is Cl.sup.−, Br.sup.− or NO.sub.3.sup.−; Y.sub.2.sup.2− is SO.sub.4.sup.2− or CO.sub.3.sup.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).sub.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.sub.2H; 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.sub.2H; and J is —[CR.sub.2].sub.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.sub.2].sub.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.sub.2CH.sub.2N(R)CH.sub.2CH.sub.2— (R is C1 to C20 hydrocarbyl) or [CH.sub.2CH(R)O].sub.nCH.sub.2CH(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.sub.2].sub.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.sub.2H; 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.sub.2H; and J is 1,2,3,4-butanetetrayl or 1,2,4,5-benzenetetrayl.

Description

MODE FOR THE INVENTION

(1) Hereinafter, the following Examples and Comparative Examples specifically describe the effect of the present invention. However, Examples below are not intended to limit the scope of the present invention but are only for exemplifying the present invention.

PREPARATION EXAMPLE 1

(2) A cobalt-Salen catalyst 6 was prepared by the following Reaction Formula 1:

(3) ##STR00018##

(4) Paraformaldehyde (0.7 g) and N-methylpiperazine (2.6 mL) were dissolved into acetonitrile (40 mL), and salicylaldehyde 2 (3.4 g) was added thereinto and stirred at 80° C. for 10 hours. When the reaction was completed, a saturated ammonium chloride aqueous solution was added thereinto to terminate the reaction, and the reactant was extracted with dichloromethane three times. An organic layer was separated and dried by magnesium sulfate, followed by filtration and distillation under reduced pressure to remove a solvent and obtain salicylaldehyde 3 containing piperazine (5.5 g). The prepared salicylaldehyde derivative 3 (3.6 g) was added into a round bottom flask wrapped with aluminum foil and was dissolved into acetonitrile (25 mL) and then 1-iododebutane (1.8 mL) was added thereinto, followed by stirring at 80° C. for 8 hours. A solvent was removed by distillation under reduced pressure, the reactant was dissolved into dichloromethane (19 mL) and silver nitrate (1.8 g) was added thereinto, followed by stirring at room temperature for 6 hours. After the reaction solution was filtered when the reaction was completed, a solvent was removed by distillation under reduced pressure to obtain a salicylaldehyde derivative 4 containing amine and an ammonium salt (3.3 g). The salicylaldehyde derivative 4 (2.7 g) containing amine and an ammonium salt and 1,2-trans-diaminocyclohexane (0.5 mL) were dissolved into dichloromethane (13 mL), followed by stirring at room temperature for 2 hours. When the reaction was completed, a solvent was removed by distillation under reduced pressure and dried to obtain a Salen derivative 5 (2.9 g). The prepared ligand 5 (0.5 g) was dissolved into dichloromethane (2 mL), and cobalt acetate tetrahydrate (144 mg) was added thereinto, followed by stirring at room temperature for 12 hours, and then lithium chloride (25 mg) was added thereinto and the reactant was oxidized by air. The produced metal complex was dissolved into dichloromethane again, an organic layer was extracted with water, and impurities were removed. After distillation under reduced pressure, a cobalt-Salen catalyst 6 containing amine and an ammonium salt (0.3 g) was obtained. Result obtained by spectroscopy experiment of the Salen derivative 5 containing amine and an ammonium salt was as follows.

(5) .sup.1H NMR (500 MHz, CDCl.sub.3)d 13.55 (2H, br s), 8.32 (2H, s), 7.26 (2H, s), 7.14 (2H, s), 3.58-3.55 (2H, d, J=15.0 Hz), 3.50 (6H, m), 3.46 (8H, m), 3.35 (2H, m), 3.21 (6H, s), 2.93-2.87 (4H, m), 2.84-2.78 (4H, m), 1.86-1.81 (4H, m), 1.76 (4H, m), 1.45-1.35 (8H, m), 1.25 (18H, s), 0.97-0.95 (6H, t, J=7.5 Hz)

PREPARATION EXAMPLE 2

(6) A cobalt-Salen catalyst 9 was prepared by the following Reaction Formula 2:

(7) ##STR00019##

(8) The salicylaldehyde derivative 3 (0.5 g) prepared by the same method as Preparation Example 1 above was added into a round bottom flask wrapped with aluminum foil and was dissolved into acetonitrile (10 mL) and then 1-bromohexane (0.3 mL) was added thereinto, followed by stirring at 80° C. for 8 hours. A solvent was removed by distillation under reduced pressure, the reactant was dissolved into dichloromethane (10 mL) and silver nitrate (0.25 g) was added thereinto, followed by stirring at room temperature for 6 hours. After the reaction solution was filtered when the reaction was completed, a solvent was removed by distillation under reduced pressure to obtain a salicylaldehyde derivative 7 containing amine and an ammonium salt (0.5 g). The salicylaldehyde derivative 7 containing amine and an ammonium salt (0.5 g) and 1,2-trans-diaminocyclohexane (0.07 mL) were dissolved into dichloromethane (6 mL), followed by stirring at room temperature for 4 hours. A solvent was removed by distillation under reduced pressure, and the reactant was washed with water and dried to obtain a Salen derivative 8 (0.5 g). The prepared ligand 8 (0.5 g) was dissolved into dichloromethane (5 mL), and cobalt acetate tetrahydrate (130 mg) was added thereinto, followed by stirring at room temperature for 12 hours, and then lithium chloride (65 mg) was added thereinto and the reactant was oxidized by air. The produced metal complex was dissolved into dichloromethane again, an organic layer was extracted with water, and impurities were removed. After distillation under reduced pressure, a cobalt-Salen catalyst 9 containing amine and an ammonium salt (0.4 g) was obtained. Result obtained by spectroscopy experiment of the Salen derivative 8 containing amine and an ammonium salt was as follows.

(9) .sup.1H NMR (500 MHz, CDCl.sub.3) d 13.56 (2H, s), 8.34 (2H, s), 7.27 (2H, s), 7.16 (2H, s), 3.73-3.37 (16H, m), 3.27 (6H, s), 2.87-2.77 (8H, m), 1.95-1.85 (4H, m), 1.74 (8H, s), 1.49-1.43 (2H, m), 1.33-1.29 (4H, m), 1.26 (26H, s), 0.99-0.97 (6H, t, J=9.0 Hz)

PREPARATION EXAMPLE 3

(10) A cobalt-Salen catalyst 12 was prepared by the following Reaction Formula 3:

(11) ##STR00020##

(12) The salicylaldehyde derivative 3 (0.5 g) prepared by the same method as Preparation Example 1 above was added into a round bottom flask wrapped with aluminum foil and was dissolved into acetonitrile (10 mL) and then 1-iodooctane (0.3 mL) was added thereinto, followed by stirring at 80° C. for 10 hours. A solvent was removed by distillation under reduced pressure, the reactant was dissolved into dichloromethane (10 mL) and silver nitrate (0.3 g) was added thereinto, followed by stirring at room temperature for 6 hours. After the reaction solution was filtered when the reaction was completed, a solvent was removed by distillation under reduced pressure to obtain a salicylaldehyde derivative 10 containing amine and an ammonium salt (0.6 g). The salicylaldehyde derivative 10 containing amine and an ammonium salt (0.6 g) and 1,2-trans-diaminocyclohexane (0.07 mL) were dissolved into dichloromethane (6 mL), followed by stirring at room temperature for 4 hours. A solvent was removed by distillation under reduced pressure, and the reactant was washed with water and dried to obtain a Salen derivative 11 (0.3 g). The prepared ligand 11 (0.3 g) was dissolved into dichloromethane (5 mL), and cobalt acetate tetrahydrate (73 mg) was added thereinto, followed by stirring at room temperature for 12 hours, and then lithium chloride (37 mg) was added thereinto and the reactant was oxidized by air. The produced metal complex was dissolved into dichloromethane again, an organic layer was extracted with water, and impurities were removed. After distillation under reduced pressure, a cobalt-Salen catalyst 12 containing amine and an ammonium salt (0.2 g) was obtained. Result obtained by spectroscopy experiment of the Salen derivative 11 containing amine and an ammonium salt was as follows.

(13) .sup.1H NMR (500 MHz, CDCl.sub.3) d 13.56 (2H, s), 8.34 (2H, s), 7.26 (2H, s), 7.15 (2H, s), 3.73-3.37 (16H, m), 3.22 (6H, s), 2.84-2.78 (8H, m), 1.93-1.86 (2H, m), 1.71 (8H, s), 1.49-1.43 (2H, m), 1.33-1.27 (24H, m), 1.26 (18H, s), 0.92-0.84 (6H, t, J=8.5 Hz)

PREPARATION EXAMPLE 4

(14) A cobalt-Salen catalyst 15 was prepared by the following Reaction Formula 4:

(15) ##STR00021##

(16) The salicylaldehyde derivative 3 (1.0 g) prepared by the same method as Preparation Example 1 above was added into a round bottom flask wrapped with aluminum foil and was dissolved into acetonitrile (20 mL) and then allyl bromide (0.4 mL) was added thereinto, followed by stirring at 80° C. for 8 hours. A solvent was removed by distillation under reduced pressure, the reactant was dissolved into dichloromethane (20 mL) and silver nitrate (0.7 g) was added thereinto, followed by stirring at room temperature for 6 hours. After the reaction solution was filtered when the reaction was completed, a solvent was removed by distillation under reduced pressure to obtain a salicylaldehyde derivative 13 containing amine and an ammonium salt (1.16 g). The salicylaldehyde derivative 13 containing amine and an ammonium salt (1.2 g) and 1,2-trans-diaminocyclohexane (0.2 mL) were dissolved into dichloromethane (15 mL), followed by stirring at room temperature for 4 hours. A solvent was removed by distillation under reduced pressure when the reaction was completed, and the reactant was washed with water and dried to obtain a Salen derivative 14 (0.7 g). The prepared ligand 14 (0.3 g) was dissolved into dichloromethane (5 mL), and cobalt acetate tetrahydrate (96 mg) was added thereinto, followed by stirring at room temperature for 12 hours, and then lithium chloride (48 mg) was added thereinto and the reactant was oxidized by air. The produced metal complex was dissolved into dichloromethane again, an organic layer was extracted with water, and impurities were removed. After distillation under reduced pressure, a cobalt-Salen catalyst 15 containing amine and an ammonium salt (128 mg) was obtained. Result obtained by spectroscopy experiment of the Salen derivative 14 containing amine and an ammonium salt was as follows.

(17) .sup.1H NMR (500 MHz, CDCl.sub.3) d 8.34 (2H, s), 7.26 (2H, s), 7.15 (2H, s), 5.95-5.92 (2H, m), 5.81-5.71 (4H, m), 4.19 (4H, d, J=6.5 Hz), 3.65 (4H, s), 3.53 (8H, s), 3.20 (6H, s), 2.95-2.86 (4H, m), 2.82-2.72 (4H, m), 2.01-1.59 (10H, m), 1.28 (18H, s)

PREPARATION EXAMPLE 5

(18) A cobalt-Salen catalyst 18 was prepared by the following Reaction Formula 5:

(19) ##STR00022##

(20) The salicylaldehyde derivative 3 (0.7 g) prepared by the same method as Preparation Example 1 above was added into a round bottom flask wrapped with aluminum foil and was dissolved into acetonitrile (10 mL) and then 1-iodo-2-methylpropane (0.5 mL) was added thereinto, followed by stirring at 80° C. for 8 hours. A solvent was removed by distillation under reduced pressure, the reactant was dissolved into dichloromethane (10 mL) and silver nitrate (0.5 g) was added thereinto, followed by stirring at room temperature for 6 hours. After the reaction solution was filtered when the reaction was completed, a solvent was removed by distillation under reduced pressure to obtain a salicylaldehyde derivative 16 containing amine and an ammonium salt (1.0 g). The salicylaldehyde derivative 16 containing amine and an ammonium salt (1.0 g) and 1,2-trans-diaminocyclohexane (0.2 mL) were dissolved into dichloromethane (10 mL), followed by stirring at room temperature for 4 hours. A solvent was removed by distillation under reduced pressure, and the reactant was washed with water and dried to obtain a Salen derivative 17 (0.7 g). The prepared ligand 17 (0.7 g) was dissolved into dichloromethane (10 mL), and cobalt acetate tetrahydrate (190 mg) was added thereinto, followed by stirring at room temperature for 12 hours, and then lithium chloride (98 mg) was added thereinto and the reactant was oxidized by air. The produced metal complex was dissolved into dichloromethane again, an organic layer was extracted with water, and impurities were removed. After distillation under reduced pressure, a cobalt-Salen catalyst 18 containing amine and an ammonium salt (0.6 g) was obtained. Result obtained by spectroscopy experiment of the Salen derivative 17 containing amine and an ammonium salt was as follows.

(21) .sup.1H NMR (500 MHz, CDCl.sub.3) d 13.53 (2H, br s), 8.34-8.31 (2H, s), 7.27 (2H, s), 7.15 (2H, s), 3.71-3.37 (16H, m), 3.27 (6H, s) 2.82-2.78 (8H, m), 2.26-2.18 (2H, m), 1.93-1.61 (6H, m), 1.48-1.44 (4H, m), 1.27-1.20 (18H, m), 1.73-1.09 (12H, m)

PREPARATION EXAMPLE 6

(22) A cobalt-Salen catalyst 19 was prepared by the following Reaction Formula 6:

(23) ##STR00023##

(24) The ligand 5 (0.5 g) prepared by the same method as Preparation Example 1 above, cobalt acetate (88 mg) and silver acetate (83 mg) were added into a round bottom flask wrapped with aluminum foil under nitrogen atmosphere and dichloromethane (2 mL) was added thereinto, followed by stirring at room temperature for 8 hours. The produced solid was removed by filtration and a solvent was removed by distillation under reduced pressure to obtain a cobalt-Salen catalyst 19 containing amine and an ammonium salt (0.5 g).

PREPARATION EXAMPLE 7

(25) A cobalt-Salen catalyst 24 was prepared by the following Reaction Formula 7:

(26) ##STR00024## ##STR00025##

(27) 1,2-trans-diaminocyclohexane 20 (10.5 mL) was dissolved into diethyl ether (200 mL) and 1M hydrogen chloride aqueous solution (87.6 mL) was slowly added thereto, followed by stirring at 25° C. for 6 hours. When the reaction was completed, the reaction solution was filtrated and the filtrated solid was vacuum dried to obtain a 1,2-trans-diaminocyclohexane derivative 21 (11.0 g). The prepared ammonium salt derivative 21 (1.3 g) and the salicylaldehyde derivative 4 (3.5 g) prepared by the same method as Preparation Example 1 above were dissolved into a mixed solution (28.0 mL) in which chloroform and methyl-tert-butyl ether are mixed at 1:3 by volume, and stirred at 25° C. for 12 hours. After the reaction solution was filtered when the reaction was completed, the filtrated solid was vacuum dried to obtain a salicylaldehyde derivative 22 containing an ammonium salt (3.1 g). The salicylaldehyde derivative 22 containing amine and an ammonium salt (2.7 g) was dissolved into dimethyl sulfoxide (15.0 mL) and a solution in which 3,5-di-tert-butyl-2-hydroxybenzaldehyde (3.9 g) is dissolved into dimethyl sulfoxide (10.0 mL) was added dropwise at 25° C. for 1 hour. When the reactant was stirred at 25° C. for 12 hours and the reaction was completed, dichloromethane (20.0 mL) was slowly added to the reaction solution to solidify the reactant. The produced solid was filtrated and the filtrated solid was vacuum dried to obtain a Salen derivative 23 (10.7 g). The prepared ligand 23 (1.0 g), cobalt acetate (245 mg) and silver acetate (231 mg) were added into under nitrogen atmosphere and dichloromethane (4 mL) was added thereinto, followed by stirring at room temperature for 6 hours. The produced solid was removed by filtration and a solvent was removed by distillation under reduced pressure to obtain a cobalt-Salen catalyst 24 containing amine and an ammonium salt (1.1 g). Result obtained by spectroscopy experiment of the Salen derivative 23 containing amine and an ammonium salt was as follows.

(28) .sup.1H NMR (500 MHz, CDCl.sub.3) d 13.55 (2H, br s), 8.40 (1H, s), 8.37 (1H, s), 7.38 (1H, s), 7.26 (1H, s), 7.14 (1H, s), 7.08 (1H, s), 3.58-3.55 (2H, d, J=15.0 Hz), 3.50 (2H, m), 3.46 (2H, m), 3.21 (3H, s), 2.93-2.87 (4H, m), 2.84-2.78 (4H, m), 1.86-1.81 (2H, m), 1.76 (2H, m), 1.45-1.35 (8H, m), 1.44 (9H, s), 1.33 (9H, s), 1.25 (9H, s), 0.97-0.95 (3H, t, J=7.5 Hz)

EXAMPLES 1 to 3

(29) Propylene oxide (PO) and each catalyst were added into a high pressure stainless steel reactor at each molar ratio as shown in the following Table 1 and the reactor was completely fastened. The high pressure reactor was slowly filled with carbon dioxide having ultra-high purity and a subsequent reaction was performed under predetermined pressure, operating temperature and time as shown in the following Table 1. After the reaction was completed, the reactant was cooled and remaining carbon dioxide was slowly discharged. After the catalyst was removed, the reactant was vacuum dried to obtain polycarbonate.

(30) TABLE-US-00001 TABLE 1 CO.sub.2 Reaction Reaction M.sub.w Example Catalyst PO:Catalyst:Ethanol Pressure Temperature Time Selectivity (g/mol) PDI TON 1 6 150,000:1:0  35 bar 65 2 h 99% 480,000 1.4 26,000 2 19 200,000:1:20 35 bar 65 4 h 99% 193,000 1.15 47,500 3 19 175,000:1:20 35 bar 65 4 h 99% 200,000 1.14 51,700

(31) As shown in Table 1, it could be appreciated that in all of Example 1 in which the molecular weight regulator (ethanol) was not used and in Examples 2 and 3 in which the molecular weight regulator in a small amount was used, poly(propylene carbonate) having a high molecular weight was prepared with high selectivity, and in addition, Examples 1 to 3 had high TON, such that productivity of poly(propylene carbonate) was also significantly high.

EXAMPLES 4 to 10

(32) Propylene oxide (PO), each catalyst and diethylene glycol were added into a high pressure stainless steel reactor at each molar ratio as shown in the following Table 2 and the reactor was completely fastened. A solvent was added thereinto as needed. The high pressure reactor was slowly filled with carbon dioxide having ultra-high purity and a subsequent reaction was performed under predetermined pressure, operating temperature and time as shown in the following Table 2. After the reaction was completed, the reaction was cooled and remaining carbon dioxide was slowly discharged. After the catalyst was removed, the reactant was vacuum dried to obtain polycarbonate.

(33) TABLE-US-00002 TABLE 2 PO PO:Catalyst:Diethylene CO.sub.2 Reaction Reaction Conversion Example Catalyst glycol Pressure Temperature Time Ratio Selectivity 4 6 10,000:1:500 30 bar 50° C. 8 h 63% 99% 5 6   25,000:1:1,300 30 bar 50° C. 18 h  99% 99% 6 9 10,000:1:500 30 bar 50° C. 8 h 16% 99% 7 12 10,000:1:500 30 bar 50° C. 8 h 11% 99% 8 15 10,000:1:500 30 bar 50° C. 8 h  4% 99% 9 18 10,000:1:500 30 bar 50° C. 8 h  7% 99% 10 19   25,000:1:1,300 30 bar 50° C. 24 h  99% 99%

COMPARATIVE EXAMPLES 1 to 4

(34) Propylene oxide (PO), each binary catalyst system of (Salen)Co compound (combination of the catalyst represented by the following Chemical Formula 23 and PPN.sup.+Cl.sup.− represented by the following Chemical Formula 24), and adipic acid were added into a high pressure stainless steel reactor at each molar ratio as shown in the following Table 3 and the reactor was completely fastened. Carbon dioxide having ultra-high purity was slowly filled into the high pressure reactor and reaction was performed under predetermined pressure, operating temperature and time as shown in the following Table 3. After the reaction was completed, the reaction was cooled and remaining carbon dioxide was slowly discharged. After the catalyst was removed, the reactant was vacuum dried to obtain poly(propylene carbonate) and physical properties of the obtained poly(propylene carbonate) were shown in the following Table 4.

(35) ##STR00026##

(36) TABLE-US-00003 TABLE 3 Formula 23:PPN.sup.+Cl.sup.−:Adipic CO.sub.2 Reaction Comparative Acid (Molar Pressure Temperature Reaction Example Catalyst Ratio) (bar) (° C.) Time (hr) 1 Chemical 2,000:1:1:0 30 25 6 Formula 23 2 Chemical 2,000:1:1:10 30 25 5 Formula 23 3 Chemical 2,000:1:1:20 30 25 5 Formula 23 4 Chemical 2,000:1:1:30 30 25 5 Formula 23

(37) TABLE-US-00004 TABLE 4 Comparative PO Conversion Example Ratio Selectivity M.sub.n PDI 1 93% 96% 9,174 1.369 2 91% 100% 7,973 1.156 3 <5% — — — 4 — — — —

(38) Comparative Examples 1 to 4 above disclose preparation of poly(alkylene carbonate) by copolymerization of carbon dioxide/epoxide using a molecular weight regulator in the presence of the existing binary catalyst system of (Salen)Co compound. It was appreciated from Tables 3 and 4 that as relative equivalent of the molecular weight regulator as compared to the catalyst system is increased, activity of the catalyst system was deteriorated, for example, PO conversion ratio was decreased, and the like. In particular, it was appreciated that in which the relative equivalent of the molecular weight regulator is 20 or more, which is a general level, PO conversion ratio was rapidly decreased to be less than 5%, such that it was determined that activity of the catalyst system was not effectively maintained. Therefore, there is a limitation in obtaining a low molecular weight of copolymer at desirable level by adding the molecular weight regulator at a general quantitative level in the presence of the existing binary catalyst system.

(39) However, according to the preparation method of the present invention disclosed in Examples of Table 2, it was appreciated that even in the case in which the relative equivalent of the molecular weight regulator as compared to the catalyst system was 20 to 1300 which is a general level, PO conversion ratio was obtained as an appropriate value. In particular, it was appreciated that even though the relative equivalent of the molecular weight regulator adopted 10 to 1300 which was a broad range, a low molecular weight of copolymer at an appropriate level was stably provided without a remarkable decrease in the catalytic activity.

(40) In addition, it was appreciated that according to Examples of Table 2, the catalyst of the present invention effectively promoted the reaction even under a relatively low copolymerization temperature condition which was 20° C. to 50° C.