KR20140070393A - Method for preparing poly carbonate - Google Patents

Abstract

The present invention relates to a producing method of polycarbonate whereby an organic transition metal catalyst without polymerization activity is oxidized in-situ, and at the same time the polycarbonate is polymerized in one pot. The producing method of polycarbonate comprises the steps of: injecting air in a reactor after putting an epoxide compound, a cobalt or bivalent chromium catalyst including salen ligands, and a chain-transfer agent in the reactor; and polymerizing epoxide and carbon dioxide by injecting carbon dioxide in the reactor.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a polycarbonate,

More particularly, the present invention relates to a method for producing polycarbonate in which an organic transition metal catalyst having no polymerization activity is oxidized in situ and polymerization of polycarbonate proceeds as a one-pot will be.

The natural environment is being destroyed due to industrial development and population increase in the world, and the economic and social pressures on pollution in the natural environment are increasing nationwide.

In particular, polymers including plastics contribute to the convenience of our daily lives and to the development of modern industries. However, as the amount of polymer used increases, the environmental pollution caused by waste polymers discarded after use is also increasing.

Recently, polycarbonate has been actively studied as an alternative to petrochemical thermoplastic materials because it is derived from renewable resources.

The bi-aliphatic polycarbonate is a biodegradable polymer which is excellent in processability and is easy to control the decomposition characteristics, and is useful as a raw material for fabrics, packaging materials, films, sheets, paints and adhesives. Aliphatic polycarbonates are prepared from epoxide compounds and carbon dioxide or by ring open polymerization of cyclic carbonates.

The method of producing an aliphatic polycarbonate from an epoxide compound and carbon dioxide is environmentally-friendly in that it does not use a poisonous compound, phosgene, and that carbon dioxide can be obtained at low cost.

Since the 1960s, many researchers have developed various types of catalysts to produce polycarbonates from epoxide compounds and carbon dioxide. Salen _{[Salen: ([H 2 Salen} = N, N '-bis (3,5-dialkylsalicylidene) -1,2-ethylenediamine] - the type of preparing an organic transition metal catalyst in a high oxidation state synthesis from epoxide ligand However, the previously prepared organic transition metal catalyst in a highly oxidized state is partially reduced during storage and storage, and is used as a catalyst for catalytic activity (see, for example, Korean Patent No. 10-0853358, Korean Patent Laid- In addition, when preparing an organic transition metal catalyst having a high oxidation state in a large amount, it is necessary to use an additional oxidizing agent or pure oxygen gas. In the case of using an oxidizing agent, There is a problem that the risk of fire is very high when an uneconomical, pure oxygen gas is used.

Therefore, in manufacturing polycarbonate, it is necessary to secure process simplicity, reduce the loss of catalyst, maximize economic efficiency, and secure safety and stability.

Korean Patent No. 10-0853358 (Aug. 13, 2008) Korean Patent Publication No. 10-2011-0112061 (October 12, 2011)

The present invention provides a process for producing polycarbonate.

The present invention

1) introducing a cobalt or chromium divalent catalyst comprising a epoxide compound, a salen ligand and a molecular weight modifier into the reactor, and injecting air; And 2) injecting carbon dioxide into the reactor to polymerize the epoxide and the carbon dioxide.

In the process for preparing a polycarbonate according to an embodiment of the present invention, the epoxide compound is selected from the group consisting of halogen, (C 1 -C 20) alkyloxy, (C 6 -C 20) aryloxy or (C 6 -C 20) (C2-C20) alkylene oxide substituted or unsubstituted with (aralkyl) oxy; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide, and the like.

In the method for producing a polycarbonate according to an embodiment of the present invention, the molecular weight modifier is a compound having a plurality of sites capable of initiating copolymerization of carbon dioxide and epoxide,

[Chemical Formula 1]

J (LH) _a

Wherein J is a hydrocarbyl a radical having 1 to 60 carbon atoms which may or may not contain an ether group, an ester group, or an amine group; Each LH is independently _{-OH, -CO 2 H, -C (} OR z) OH, -OC (R z) OH, -NHR z, -NHC (O) R z, -NHC = NR z, -NR ^{z C = NH, -NR z C} (NR z 2) = NH, -NHC (NR z 2) = NR z, -NHC (O) OR z, -NHC (O) NR z 2, -C (O) ^{NHR z, -C (S) NHR} z, -OC (O) NHR z, -OC (S) NHR z, -SH, -C (O) SH, -B (OR z) OH, -P (O) ^{_{b (R z) c (OR}} z) d (O) e H, -OP (O) b (R z) c (OR z) d (O) e H, -N (R z) OH, -ON ( R ^z ) H, = NOH or = NN (R ^z ) H; Each R ^z is independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) heteroaliphatic alkyl, 3 to 12 membered heterocyclic or (C6-C12) aryl; a is an integer of 1 to 10 and when a is 2 or more, LH may be the same or different from each other; b and c are each independently 0 or 1, d is 0, 1 or 2, e is 0 or 1, and the sum of b, c and d is 1 or 2.

In the production method of the polycarbonate in accordance with an embodiment of the present invention, a molecular weight regulator of the formula (1) is a LH is -OH or -CO ₂ H; and a may be an integer of 1 to 4.

In the process for preparing a polycarbonate according to an embodiment of the present invention, the cobalt or chromium divalent catalyst comprising the Salen ligand may be represented by the following formula 2:

(2)

In Formula 2,

M is cobalt divalent or chromium divalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R ', R " and R "' are independently of each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl;

Among the above R ', R''andR''' Two of which may be connected to each other to form a ring; Cyano; Nitro; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; And (C6-C20) arylcarbonyl.

In the process for preparing a polycarbonate according to an embodiment of the present invention, the cobalt or chromium divalent catalyst comprising the salen ligand may be represented by the following formula 3:

(3)

In Formula 3,

M is cobalt divalent or chromium divalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R ¹ To R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl;

The R ¹ To R ¹⁰ medium Two of which may be connected to each other to form a ring;

The R ¹ To R ¹⁰ and Q is substituted with a proton radical selected from the group consisting of the following formulas a, b and c;

X ^- are independently of one another a halogen anion; HCO ₃ ^- ; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^- ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;

Z is a nitrogen or phosphorus atom;

R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl; Two of R ²¹ , R ²² and R ²³ or R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ Two of which may be connected to each other to form a ring;

R ⁴¹ , R ⁴² and R ⁴³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl; Two of R ⁴¹ , R ⁴² and R ⁴³ may be connected to each other to form a ring;

X 'is an oxygen atom, a sulfur atom or N-R wherein R is (C1-C20) alkyl;

n is < ^{RTI ID =} To Lt; ¹⁰ > and Q is a positive integer which is the total number of proton terminals included;

The nitrogen atom of the imine may coordinate to or coordinate to M.

In the method for producing a polycarbonate according to an embodiment of the present invention, in the molecular weight modifier of Formula 1, a is 1; And LH is -OH or -CO ₂ H; J is - [CR ⁵¹ R ⁵² ] _n -CR ⁵³ R ⁵⁴ R ⁵⁵ , phenyl or naphthyl; n is an integer from 0 to 20; R ⁵¹ to R ⁵⁵ may be the same or different and may be hydrogen, methyl, ethyl, propyl or butyl.

In the method for producing a polycarbonate according to an embodiment of the present invention, in the molecular weight modifier of Formula 1, a is 2; LH it may be the same or different and is -OH or -CO ₂ H; J is - [CR ⁵¹ R ⁵² ] _n- , para-phenylene, meta-phenylene, o-phenylene, 2,6-naphthalenediyl, -CH ₂ CH ₂ N (R ⁵⁶ ) CH ₂ CH ₂ - Or - [CH ₂ CH (R ⁵⁶ ) O] _m CH ₂ CH (R) -; n is an integer from 1 to 20; R ⁵¹ , R ⁵² and R ⁵⁶ , which may be the same or different, are hydrogen, methyl, ethyl, propyl or butyl; and m may be an integer of 1 to 10.

In the method for producing a polycarbonate according to an embodiment of the present invention, in the molecular weight modifier of Formula 1, a is 3; LH is a -CO ₂ H; J may be 1,2,3-propanetriyl, 1,2,3-benzenetriyl, 1,2,4-benzenetriyl or 1,3,5-benzenetriyl.

In the method for producing a polycarbonate according to an embodiment of the present invention, in the molecular weight modifier of Formula 1, a is 4; LH is a -CO ₂ H; J may be 1,2,3,4-butanetetrayl or 1,2,4,5-benzenetetrayl.

In the method for producing polycarbonate according to an embodiment of the present invention, a solvent may be further added in the step 1).

In the process for producing a polycarbonate according to an embodiment of the present invention, the solvent may be at least one selected from the group consisting of aromatic hydrocarbons, halogenated hydrocarbons, ethers and esters.

In the process for preparing a polycarbonate according to an embodiment of the present invention, the solvent may be at least one selected from the group consisting of toluene, dichloromethane, dichloroethane, tetrahydrofuran and ethyl acetate.

In the process for preparing a polycarbonate according to an embodiment of the present invention, the mole ratio of the epoxide compound: catalyst may be 100: 1 to 1,000,000: 1.

The method for producing polycarbonate according to the present invention does not require a separate catalyst preparation step, thereby ensuring the simplicity of the entire process and reducing the loss of catalyst that can be generated in the production process, There is an advantage of reducing the cost.

In addition, the transition metal catalyst in a highly oxidized state used in the polymerization may be partially reduced during storage and storage of the catalyst when it is prepared in advance, and the catalytic activity may be lowered. On the other hand, When the catalyst is oxidized in situ, it is not necessary to pay careful attention to the storage and storage of the catalyst, and stability is ensured because the reduction of activity due to reduction of the catalyst does not occur.

Further, in order to mass-produce an organic transition metal catalyst having a high oxidation state to be used for polymerization, an additional oxidizing agent or pure oxygen gas must be used. In the case of using an oxidizing agent, a catalyst separation process is required after the reaction, It is difficult to secure stability because of high fire risk. On the other hand, in the present invention, cobalt or chromium 2, which is merely metalized and has no polymerization activity, is safe because it is used for polymerization by in-situ oxidation of the catalyst using air as a low-fire mixer air.

The present invention provides a method of making a polycarbonate, and more specifically comprises the following two steps:

1) introducing a cobalt or chromium divalent catalyst comprising a epoxide compound, a salen ligand and a molecular weight modifier into the reactor, and injecting air;

2) a step of injecting carbon dioxide into the reactor to polymerize the epoxide and carbon dioxide.

The process for preparing polycarbonate of the present invention is characterized in that a cobalt or chromium 2 catalyst containing a Salen ligand is converted into a metallized cobalt or chromium 2 catalyst having no polymerization activity when the catalyst is added thereto, in-situ, and at the same time to produce a polycarbonate having a high molecular weight and a narrow molecular weight distribution, it is possible to prepare a transition metal catalyst of high oxidation state (Korean Patent Publication No. 10-2011-0112061) And it is possible to prevent the problem that the catalyst is partially reduced during storage and storage of the catalyst and the catalytic activity is lowered.

That is, since the method for producing polycarbonate of the present invention does not use a catalyst in a high oxidation state, there is no need to pay careful attention to the storage and storage of the catalyst, and since the reduction of activity due to the reduction of the catalyst does not occur, do.

In the process for producing a polycarbonate according to an embodiment of the present invention, air is injected in the step 1) in order to use the catalyst for in-situ oxidation of a cobalt or chromium 2 catalyst, do. On the other hand, in order to mass-produce a high-oxidation organic transition metal catalyst used in the conventional polymerization, it is necessary to use an additional oxidizing agent or a pure oxygen gas. In the case of using an oxidizing agent, There is a problem in that it is difficult to ensure stability since the risk of fire is high when using gas. In order to solve this problem, in the present invention, cobalt or chromium 2, which is merely metalized and has no polymerization activity, is advantageously used for polymerization by in-situ oxidation using air as a low-risk air-fuel mixture.

The pressure of the air injected in the step 1) is not limited, but preferably from 1 to 30 atm.

The chain transfer agent according to an embodiment of the present invention may be any compound having a plurality of sites capable of initiating copolymerization of carbon dioxide and epoxide, desirable:

[Chemical Formula 1]

J (LH) _a

Wherein J is a hydrocarbyl a radical having 1 to 60 carbon atoms which may or may not contain an ether group, an ester group, or an amine group; Each LH is independently _{-OH, -CO 2 H, -C (} OR z) OH, -OC (R z) OH, -NHR z, -NHC (O) R z, -NHC = NR z, -NR ^{z C = NH, -NR z C} (NR z 2) = NH, -NHC (NR z 2) = NR z, -NHC (O) OR z, -NHC (O) NR z 2, -C (O) ^{NHR z, -C (S) NHR} z, -OC (O) NHR z, -OC (S) NHR z, -SH, -C (O) SH, -B (OR z) OH, -P (O) ^{_{b (R z) c (OR}} z) d (O) e H, -OP (O) b (R z) c (OR z) d (O) e H, -N (R z) OH, -ON ( R ^z ) H, = NOH or = NN (R ^z ) H; Each R ^z is independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) heteroaliphatic alkyl, 3 to 12 membered heterocyclic or (C6-C12) aryl; a is an integer of 1 to 10 and when a is 2 or more, LH may be the same or different from each other; b and c are each independently 0 or 1, d is 0, 1 or 2, e is 0 or 1, and the sum of b, c and d is 1 or 2.

Examples of the molecular weight regulator of Formula 1 include polyhydric alcohols, specifically, diols, triols, tetraols, and the like. Specific examples of the diols include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, Pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6- Diol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2- Diol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Hexene diethanol, 4,4 '- (1-methylethylidene) bis [cyclohexanol], 2,2'-methylenebis [phenol], 4,4'- methylenebis [phenol] - (phenylmethylene) bis [phenol], 4,4 '- (diphenylmethylene) bis [phenol], 4,4' , 2-cyclohexanediyl) bis [phenol], 4,4 '- (1,3-cyclohexanediyl) bis [phenol] 4,4'- (1-phenylethylidene) bis [phenol], 4,4'- (1,4-cyclohexanediyl) bis [phenol], 4,4'-ethylidenebis 4'-cyclohexylidenebis [phenol], 4,4 '- (1-methylethylidene) bis [phenol] Propylidene) bis [phenol], 4,4'- (1-ethylpropylidene) bis [phenol], 4,4'-cyclohexylidenebis [phenol], 4,4 '- , 10-tetraoxaspiro [5.5] undecane-3,9-diydido-2,1-ethanediyl) bis [phenol], 1,2-benzene dimethanol, 1,3- Phenylene] bis [phenol], 4,4 '- [1,4-phenylenebis (1-methylene) (1-methylidene)] bis [phenol], phenolphthalein, 4,4 '- (1-methylidene) Methylethyl) phenol] and 2,2'-methylenebis [4-methyl-6- (1-methylethyl) phenol]. Specific examples of the triols include trimethylol ethane; Trimethylol propane; Glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; Tris (2-hydroxyethyl) isocyanurate; Hexahydro-1,3,5-tris (hydroxyethyl) -s-triazine; 6-methylheptane-1,3,5-triol; Polypropylene oxide triol; And aliphatic triols having a molecular weight of less than 500 such as polyester triols. Specific examples of the tetraol include: erythritol, pentaerythritol; 2,2'-dihydroxymethyl-1,3-propanediol; And 2,2 '- (oxydimethylene) bis- (2-ethyl-1,3-propanediol).

Examples of the molecular weight regulator of Formula 1 include diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly (ethylene glycol) (preferably having a number average molecular weight of 220 to 2000 g / mol), dipropylene glycol, tri Propylene glycol, and high-grade poly (propylene glycol) (preferably having a number average molecular weight of 234 to about 2000 g / mol).

The molecular weight regulator of Formula 1 may be exemplified by hydroxy acids, specifically, alpha-hydroxy acids or beta-hydroxy acids. Specific examples of the alpha-hydroxy acid include glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid and mandelic acid. Specific examples of the beta -hydroxy acid include 3-hydroxypropionic acid, DL 3-hydroxybutyric acid, D-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3- Salicylic acid and derivatives of salicylic acid.

Examples of the molecular weight regulator of Formula 1 include diacids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid and azelaic acid .

The molecular weight control of the formula 1 according to one embodiment of the present invention zero, LH is an -OH or -CO ₂ H; and a is an integer of 1 to 4 is more preferable.

In the molecular weight modifier of Formula 1 according to an embodiment of the present invention, a is 1; And LH is -OH or -CO ₂ H; J is - [CR ⁵¹ R ⁵² ] _n -CR ⁵³ R ⁵⁴ R ⁵⁵ , phenyl or naphthyl; n is an integer from 0 to 20; R ⁵¹ to R ^55, which may be the same or different, are hydrogen, methyl, ethyl, propyl or butyl.

In the method for producing a polycarbonate according to an embodiment of the present invention, in the molecular weight modifier of Formula 1, a is 2; LH it may be the same or different and is -OH or -CO ₂ H; J is - [CR ⁵¹ R ⁵² ] _n- , para-phenylene, meta-phenylene, o-phenylene, 2,6-naphthalenediyl, -CH ₂ CH ₂ N (R ⁵⁶ ) CH ₂ CH ₂ - Or - [CH ₂ CH (R ⁵⁶ ) O] _m CH ₂ CH (R) -; n is an integer from 1 to 20; R ⁵¹ , R ⁵² and R ⁵⁶ , which may be the same or different, are hydrogen, methyl, ethyl, propyl or butyl; m is an integer of 1 to 10;

In the method for producing a polycarbonate according to an embodiment of the present invention, in the molecular weight modifier of Formula 1, a is 3; LH is a -CO ₂ H; J is 1,2,3-propanetriyl, 1,2,3-benzenetriyl, 1,2,4-benzenetriyl or 1,3,5-benzenetriyl.

In the method for producing a polycarbonate according to an embodiment of the present invention, in the molecular weight modifier of Formula 1, a is 4; LH is a -CO ₂ H; J is 1,2,3,4-butanetetrayl or 1,2,4,5-benzenetetrayl.

The molecular weight regulator according to an embodiment of the present invention is most preferably mixed with methanol, acetic acid, adipic acid, succinic acid, phthalic acid alone or in combination with other molecular weight regulators.

The cobalt or chromium divalent catalyst comprising the Salen ligand according to an embodiment of the present invention may be any cobalt or chromium 2 catalyst including a known salen ligand, Or 3 is a cobalt or chromium 2 catalyst comprising a Salen ligand,

(2)

In Formula 2,

M is cobalt divalent or chromium divalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R ', R " and R "' are independently of each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl;

Among the above R ', R''andR''' Two of which may be connected to each other to form a ring; Cyano; Nitro; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; And (C6-C20) arylcarbonyl.

(3)

In Formula 3,

M is cobalt divalent or chromium divalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R ¹ To R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl;

The R ¹ To R ¹⁰ medium Two of which may be connected to each other to form a ring;

The R ¹ To R ¹⁰ and Q is substituted with a proton radical selected from the group consisting of the following formulas a, b and c;

X ^- are independently of one another a halogen anion; HCO ₃ ^- ; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^- ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;

Z is a nitrogen or phosphorus atom;

R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl; Two of R ²¹ , R ²² and R ²³ or R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ Two of which may be connected to each other to form a ring;

R ⁴¹ , R ⁴² and R ⁴³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl; Two of R ⁴¹ , R ⁴² and R ⁴³ may be connected to each other to form a ring;

X 'is an oxygen atom, a sulfur atom or N-R wherein R is (C1-C20) alkyl;

n is < ^{RTI ID =} To Lt; ¹⁰ > and Q is a positive integer which is the total number of proton terminals included;

The nitrogen atom of the imine may coordinate to or coordinate to M.

In a cobalt or chromium divalent catalyst comprising the Salen ligand of Formula 2 or 3, Q is a divalent radical having two radicals capable of bonding two nitrogen atoms, And is preferably a (C1-C30) hydrocarbon di-radical having at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom, (C 1 -C 20) alkylene, (C 2 -C 20) alkenylene, (C 2 -C 20) alkynylene, (C 3 -C 20) cycloalkylene or Nylene, cycloalkylene and arylene may or may not contain at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom. The above Q is more preferably trans-1, 2-cyclohexylene, phenylene or ethylene.

In the catalyst of Formula 2, R '' and R '' 'may be connected to each other to form an aromatic ring, and the aromatic ring formed may be substituted with halogen; Cyano; Nitro; (C1-C20) alkyl; (C1-C20) alkyl substituted by halogen atoms; (C1-C20) alkyl (C6-C20) aryl; (C6-C20) aryl (C1-C20) alkyl; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; And (C6-C20) arylcarbonyl.

In the catalyst of Formula 3, more preferably, the R < ^{1 >} To R ¹⁰ is independently from each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 1 -C 20) alkyl (C 6 -C 20) aryl, (C6-C60) aryloxy, formyl, (C1-C20) alkylcarbonyl, (C6-C20) arylcarbonyl, Gt; is a metalloid radical of a Group 14 metal substituted with < RTI ID = 0.0 > R ^& To R ⁸ is - [YR ⁴⁴ _{3 -a} {(CR ⁴⁵ R ⁴⁶ ) _b N ⁺ R ²¹ R ²² R ²³ } _a ] and Y is C or Si; R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ²¹ , R ²² And R < ²³ > are independently from each other hydrogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, and R < ²¹ > Two of R < ²² > and R < ²³ > may be connected to each other to form a ring; a is an integer of 1 to 3, b is an integer of 1 to 20; n is < ^{RTI ID =} To The total number of quaternary ammonium salts contained in R ⁸ is a positive integer.

In the catalyst of Formula 3, more preferably, X < ^- > is independently a halogen anion; HCO ₃ ^- ; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^- ; (C6-C20) aryloxy anion; Nitro-substituted (C6-C20) aryloxy anion; (C1-C20) alkylcarboxy anion; (C6-C20) arylcarboxy anion; (C1-C20) alkoxy anion; (C1-C20) alkylcarbonate anion; (C6-C20) aryl carbonate anion; (C1-C20) alkylsulfonate anion; (C1-C20) alkyl amido anion; (C6-C20) arylamido anion; (C1-C20) alkylcarbamate anion; (C6-C20) aryl carbamate anion.

In the process for preparing a polycarbonate according to an embodiment of the present invention, the epoxide compound is selected from the group consisting of halogen, (C 1 -C 20) alkyloxy, (C 6 -C 20) aryloxy or (C 6 -C 20) (C2-C20) alkylene oxide substituted or unsubstituted with an aralkyloxy group; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide.

In the process for producing polycarbonate according to the present invention, specific examples of the epoxide compound include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, But are not limited to, ethylene oxide, octadecene oxide, butadiene monoxide, 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether , t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3 - epoxide norbornene, limonene oxide, dieldrin, 2,3-epoxide propylbenzene, styrene oxide Phenylpropylene oxide, stilbene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyloxirane, glycidyl-methylphenyl ether, chlorophenyl- 3-epoxide propyl ether, epoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether, and the like.

In the process for producing a polycarbonate according to an embodiment of the present invention, not only can the bulk polymerization be carried out using the epoxide compound itself as a solvent, but a solvent can be further included in the reaction medium and used for polymerization. That is, it is possible to further introduce a solvent in the step 1). By introducing a solvent, degradation of the activity due to viscosity during the polymerization reaction can be suppressed and the quenching and separation process of the catalyst can be controlled Do.

In the process for producing a polycarbonate according to an embodiment of the present invention, the solvent is at least one selected from the group consisting of aromatic hydrocarbons, halogenated hydrocarbons, ethers and esters, and specific examples thereof include benzene, toluene, And aromatic hydrocarbons such as toluene, xylene and the like, aromatic hydrocarbons such as chloromethane, methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethyl chloride, trichloroethane, 1- chloropropane, Halogenated hydrocarbons such as 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, chlorobenzene and bromobenzene, ethers such as tetrahydrofuran, diethyl ether, diphenyl ether or dioxane, Esters such as acetate, butyl acetate, methyl benzoate, and the like, or a combination of two or more thereof There.

In the process for producing a polycarbonate according to an embodiment of the present invention, the solvent is most preferably one or more selected from the group consisting of toluene, dichloromethane, dichloroethane, tetrahydrofuran and ethyl acetate.

In the method for producing a polycarbonate according to an embodiment of the present invention, the pressure of the carbon dioxide in the step 2) is from 100 atm to 100 atm, preferably from 5 to 30 atm. The internal temperature of the reactor after the injection of carbon dioxide, that is, the polymerization temperature is 100 ° C or less, preferably 20 ° C to 100 ° C, more preferably 20 ° C to 60 ° C, and is polymerized for 5 to 20 hours.

In the process for preparing a polycarbonate according to an embodiment of the present invention, the molar ratio of the epoxide compound: divalent catalyst (Formula 2 or 3) may be 100: 1 to 1,000,000: 1, 50,000: 1. The epoxide compound can be used as a polymerization agent and as a solvent. If the mole ratio of the epoxide compound to the divalent catalyst is out of the range, the concentration of the reactant becomes too small and the polymerization activity of the catalyst is deteriorated.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to specific examples and comparative examples. However, these examples are merely intended to clarify the present invention and are not intended to limit the scope of the present invention.

[Production Example 1]

Catalyst 1 was prepared according to J. Am . Chem . Soc . 2002 , 124 , and 1307, respectively. Catalyst 2 was prepared and used in accordance with Korean Patent B1 0853358.

[Example 1] Catalyst 1 In-situ oxidation and Polymerization

Propylene oxide (10 mL), catalyst 1 (43 mg), bis (triphenylphospho-ranylidene) ammonium chloride (41 mg) and adipic acid (104 mg) as a molecular weight regulator were charged in a 50 mL reactor, . After injecting 10 bar of air, the mixture was stirred at room temperature for 2 hours. Then, 20 bar of carbon dioxide was further added and stirred for 41 hours. After the reaction is completed, the reactor is cooled and the gas pressure of carbon dioxide and air is removed to terminate the reaction. Malonic acid is added to the obtained mucus-containing solution to prevent decomposition of the resulting polymer. The conversion of reactants and selectivity for polymer formation were calculated by ¹ H-NMR. The molecular weight of the polymer produced by GPC was measured. The results are shown in Table 1 below.

[Example 2] Catalyst 2 In-situ oxidation and polymerization

Propylene oxide (10 mL) and catalyst 2 (48.5 mg), adipic acid (626 mg) as a molecular weight regulator, and toluene (10 mL) were placed in a 50 mL stainless bomb reactor and the reactor was assembled. After injecting 10 bar of air, the mixture was stirred at room temperature for 2 hours. 20 bar of carbon dioxide was further introduced, and the inside temperature of the reactor was maintained at 50 캜 for 15 hours. At this time, the total pressure of the reactor is 30 bar. After the reaction is completed, the reactor is cooled and the gas pressure of carbon dioxide and air is removed to terminate the reaction. Malonic acid is added to the obtained mucus-containing solution to prevent decomposition of the resulting polymer. The conversion of reactants and selectivity for polymer formation were calculated by ¹ H-NMR. The molecular weight of the polymer produced by GPC was measured. The results are shown in Table 1 below.

[Comparative Example 1] Catalyst 1 In-situ oxidation and polymerization

The same procedure as in Example 1 was carried out except that the molecular weight regulator was not used, and the results are shown in Table 1 below.

Example catalyst PO / catalyst Molecular Weight
Modulator Reaction temperature (캜) Reaction time PO conversion rate
/ Selectivity Example 1 One 2000/1 Adipic acid (10 eq) RT 41h 26% / 83% Example 2 2 5000/1 Adipic acid (150 eq) 50 15h 90% / 97% Comparative Example 1 One 2000/1 X RT 21h -

From the results shown in the above Table 1, it is possible to prepare a catalyst having activity through in-situ oxidation from a divalent catalyst having no activity, and at the same time to be able to polymerize. Particularly in the case of the catalyst 2 of Example 2, propylene oxide And a catalyst having a molar ratio of 5000: 1, the polycarbonate can be produced with high conversion and selectivity. On the other hand, in the case of Comparative Example 1, even though the same catalyst 1 as the divalent catalyst of Example 1 was used, the polycarbonate was not produced without using the molecular weight regulator.

Therefore, it is necessary to use a molecular weight regulator in order to prepare a catalyst having activity through in-situ oxidation from a divalent catalyst having no activity and to enable polymerization at the same time.

[Example 3] Propylene oxide conversion by solvent

Propylene oxide (10 mL) and catalyst 2 (118 mg), adipic acid (626 mg) as a molecular weight regulator and the solvent (10 mL) shown in the following Table 2 were placed in a 50 mL stainless bomb reactor and the reactor was assembled. After injecting 10 bar of air, the mixture was stirred at room temperature for 2 hours. After 20 bar of carbon dioxide was added, the reactor was maintained at a constant temperature for 15 hours with stirring. After the reaction is completed, the reactor is cooled and the pressure of the carbon dioxide is removed to terminate the reaction. Malonic acid is added to the obtained mucus-containing solution to prevent decomposition of the resulting polymer. The conversion of reactants and selectivity for polymer formation were calculated by ¹ H-NMR. The molecular weight of the polymer produced by GPC was measured. The results are shown in Table 2 below.

[Examples 4 to 6]

The same procedure as in Example 3 was carried out, and the effects of various solvents were shown in Table 2 below.

Example menstruum PO / catalyst Temperature
(° C) pressure time PO conversion rate
/ Selectivity Mw / Mn PDI 3 DCE 2000: 1 50 20bar 15h > 99% / 86% 2172/1871 1.16 4 Toluene 2000: 1 50 20bar 15h > 99% / 88% 2509/2294 1.09 5 THF 2000: 1 50 20bar 15h 99% / 89% 2448/2247 1.09 6 EA 2000: 1 50 20bar 15h > 99% / 89% 2459/2249 1.09

[Example 7] Propylene oxide conversion

Propylene oxide (10 mL) and catalyst 2 (60 mg), adipic acid (626 mg) as a molecular weight regulator, and dichloromethane (10 mL) were placed in a 50 mL stainless bomb reactor and the reactor was assembled. After injecting 10 bar of air, the mixture was stirred at room temperature for 2 hours. Thereafter, 20 bar of carbon dioxide was further charged, and the inside temperature of the reactor was kept at 50 캜 for 5 hours and then stirred. After the reaction is completed, the reactor is cooled and the pressure of the carbon dioxide is removed to terminate the reaction. Malonic acid is added to the obtained mucus-containing solution to prevent decomposition of the resulting polymer. The conversion of reactants and selectivity for polymer formation were calculated by ¹ H-NMR. The molecular weight of the polymer produced by GPC was measured. The results are shown in Table 3 below.

[Examples 8 to 11] Propylene oxide conversion

The effects of solvents, catalyst equivalents and temperatures in the same manner as in Example 7 are shown in Table 3 below.

Example menstruum PO / catalyst Temperature
(° C) pressure time PO conversion rate / selectivity Mn PDI 7 DCM 4000: 1 50 20bar 5h 75% / 99% 2103 1.15 8 Toluene 4000: 1 50 20bar 5h 89% / 99% 2305 1.16 9 Toluene 5000: 1 50 20bar 15h 98% / 96% 2294 1.09 10 Toluene 5000: 1 70 20bar 15h 48% / 47% 1863 1.09 11 Toluene 10000: 1 50 20bar 15h 76% / 96% 2249 1.09

[Example 12] Reactivity according to presence or absence of solvent

Propylene oxide (10 mL) and catalyst 2 (48.5 mg), adipic acid (626 mg) as a molecular weight regulator, and solvent (10 mL) were placed in a 50 mL stainless bomb reactor and the reactor was assembled. After injecting 10 bar of air, the mixture was stirred at room temperature for 2 hours. Thereafter, 20 bar of carbon dioxide was further charged, and the inside temperature of the reactor was maintained at 50 캜 for 15 hours. After the reaction is completed, the reactor is cooled and the pressure of the carbon dioxide is removed to terminate the reaction. Malonic acid is added to the obtained mucus-containing solution to prevent decomposition of the resulting polymer. The conversion of reactants and selectivity for polymer formation were calculated by ¹ H-NMR. The molecular weight of the polymer produced by GPC was measured. The results are shown in Table 4 below.

[Examples 13 to 16] Reactivity according to presence or absence of solvent

The experiment was carried out in the same manner as in Example 12, and the effect according to the amount of solvent used is shown in Table 4 below.

Example PO / catalyst toluene PO Conversion Rate (%) PPC diol selectivity (%) 12 5000: 1 10 mL 98 95 13 5000: 1 5 mL 99 94 14 5000: 1 2 mL 90 90 15 5000: 1 0 96 86 16 10000: 1 X (20 mL of PO) 90 86

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the invention as defined by the appended claims. It will be possible to carry out various modifications. Therefore, modifications of the embodiments of the present invention will not depart from the scope of the present invention.

Claims (14)

1) introducing a cobalt or chromium divalent catalyst comprising a epoxide compound, a salen ligand and a molecular weight modifier into the reactor, and injecting air;
2) injecting carbon dioxide into the reactor to polymerize the epoxide and carbon dioxide;
≪ / RTI >
The method according to claim 1,
The epoxide compound is a (C2-C20) alkoxy substituted or unsubstituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6- Alkylene oxides; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide. ≪ RTI ID = 0.0 > 21. < / RTI >
The method according to claim 1,
Wherein the molecular weight modifier is represented by the following formula (1).
[Chemical Formula 1]
J (LH) _a
[Wherein J is a hydrocarbyl a radical having 1 to 60 carbon atoms, with or without an ether group, an ester group, or an amine group; Each LH is independently _{-OH, -CO 2 H, -C (} OR z) OH, -OC (R z) OH, -NHR z, -NHC (O) R z, -NHC = NR z, -NR ^{z C = NH, -NR z C} (NR z 2) = NH, -NHC (NR z 2) = NR z, -NHC (O) OR z, -NHC (O) NR z 2, -C (O) ^{NHR z, -C (S) NHR} z, -OC (O) NHR z, -OC (S) NHR z, -SH, -C (O) SH, -B (OR z) OH, -P (O) ^{_{b (R z) c (OR}} z) d (O) e H, -OP (O) b (R z) c (OR z) d (O) e H, -N (R z) OH, -ON ( R ^z ) H, = NOH or = NN (R ^z ) H; Each R ^z is independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) heteroaliphatic alkyl, 3 to 12 membered heterocyclic or (C6-C12) aryl; a is an integer of 1 to 10 and when a is 2 or more, LH may be the same or different from each other; b and c are each independently 0 or 1, d is 0, 1 or 2, e is 0 or 1, and the sum of b, c and d is 1 or 2.
The method of claim 3,
In Formula 1, LH is an -OH or -CO ₂ H; and a is an integer of 1 to 4.
The method according to claim 1,
Wherein the cobalt or chromium divalent catalyst comprising the salen ligand is represented by the following formula (2).
(2)

[In the formula (2)
M is cobalt divalent or chromium divalent;
A is an oxygen or sulfur atom;
Q is a diradical linking two nitrogen atoms;
R ', R " and R "' are independently of each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl;
Among the above R ', R''andR''' Two of which may be connected to each other to form a ring; Cyano; Nitro; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; And (C6-C20) arylcarbonyl.
The method according to claim 1,
Wherein the cobalt or chromium divalent catalyst comprising the Salen ligand is represented by the following formula (3).
(3)

[Formula 3]
M is cobalt divalent or chromium divalent;
A is an oxygen or sulfur atom;
Q is a diradical linking two nitrogen atoms;
R ¹ To R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl;
The R ¹ To R ¹⁰ medium Two of which may be connected to each other to form a ring;
The R ¹ To R ¹⁰ and Q is substituted with a proton radical selected from the group consisting of the following formulas a, b and c;

X ^- are independently of one another a halogen anion; HCO ₃ ^- ; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^- ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;
Z is a nitrogen or phosphorus atom;
R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl; Two of R ²¹ , R ²² and R ²³ or R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ Two of which may be connected to each other to form a ring;
R ⁴¹ , R ⁴² and R ⁴³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C2-C20) alkenyl; (C2-C20) alkenyl including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; Or a metalloid radical of a Group 14 metal substituted with (C1-C20) alkyl or (C6-C20) aryl; Two of R ⁴¹ , R ⁴² and R ⁴³ may be connected to each other to form a ring;
X 'is an oxygen atom, a sulfur atom or NR (where R is (C1-C20) alkyl);
n is < ^{RTI ID =} To Lt; ¹⁰ > and Q is a positive integer which is the total number of proton terminals included;
The nitrogen atom of the imine may coordinate to or coordinate to M.]
The method of claim 3,
In Formula 1, a is 1; And LH is -OH or -CO ₂ H; J is - [CR ⁵¹ R ⁵² ] _n -CR ⁵³ R ⁵⁴ R ⁵⁵ , phenyl or naphthyl; n is an integer from 0 to 20; R ⁵¹ to R ^55, which may be the same or different, are hydrogen, methyl, ethyl, propyl or butyl.
The method of claim 3,
In Formula 1, a is 2; LH it may be the same or different and is -OH or -CO ₂ H; J is - [CR ⁵¹ R ⁵² ] _n- , para-phenylene, meta-phenylene, o-phenylene, 2,6-naphthalenediyl, -CH ₂ CH ₂ N (R ⁵⁶ ) CH ₂ CH ₂ - Or - [CH ₂ CH (R ⁵⁶ ) O] _m CH ₂ CH (R) -; n is an integer from 1 to 20; R ⁵¹ , R ⁵² and R ⁵⁶ , which may be the same or different, are hydrogen, methyl, ethyl, propyl or butyl; and m is an integer of 1 to 10.
The method of claim 3,
In Formula 1, a is 3; LH is a -CO ₂ H; Wherein J is 1,2,3-propanetriyl, 1,2,3-benzenetriyl, 1,2,4-benzenetriyl or 1,3,5-benzenetriyl. Way.
The method of claim 3,
In Formula 1, a is 4; LH is a -CO ₂ H; And J is 1,2,3,4-butanetetrayl or 1,2,4,5-benzenetetrayl.
The method according to claim 1,
Wherein a solvent is further added in the step 1).
12. The method of claim 11,
Wherein the solvent is at least one selected from the group consisting of aromatic hydrocarbons, halogenated hydrocarbons, ethers and esters.
13. The method of claim 12,
Wherein the solvent is at least one selected from the group consisting of toluene, dichloromethane, dichloroethane, tetrahydrofuran and ethyl acetate.
The method according to claim 1,
Wherein the mole ratio of the cobalt or chromium divalent catalyst comprising the epoxide compound: Salen ligand is from 100: 1 to 1,000,000: 1.