Double metal cyanide catalyst and method for producing same

Abstract

One aspect of the present invention provides a double metal cyanide catalyst with excellent catalytic activity and a method for producing the same. Specifically, the double metal cyanide catalyst according to one aspect is characterized by being produced using a complexing agent including tert-butanol, a linear or cyclic (C2-C12) aliphatic polyhydric alcohol, and a polyalkylene glycol.

Description

[Technical Field]

[0001] The present invention relates to a double metal cyanide (DMC) catalyst having excellent catalytic activity and a method for producing the same. [Background technology]

[0002] Polyether carbonate polyols are widely used as materials for adhesives, packaging materials, coating materials, etc., and are attracting attention as polymeric materials that are particularly easily biodegradable. Furthermore, producing polyether carbonate polyols by reacting an epoxide compound with carbon dioxide is an environmentally friendly production method that utilizes greenhouse gases without using toxic compounds, and research into the development of catalysts applicable to this reaction is ongoing.

[0003] On the other hand, double metal cyanide (DMC) catalysts are used in the polymerization of polymer products such as polyether, polyester, and polyetherester polyols. Compared to the use of conventional basic catalysts, DMC catalysts have the advantage of being able to produce high-quality polymer products with low unsaturation and high molecular weight.

[0004] However, when a DMC catalyst is applied to a method for producing polyether carbonate polyol from the reaction of an epoxide compound with carbon dioxide, the catalytic activity is still insufficient, a relatively large amount of catalyst is used, and there are limitations such as the need for a process for removing catalyst residues remaining after the polymerization reaction. Furthermore, when attempting to reduce the amount of catalyst used, there are problems such as a longer polymerization reaction time and a deterioration in the quality of the polymer product, which reduces productivity and makes it difficult to commercialize. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of one aspect of the present invention is to provide a double metal cyanide catalyst having excellent catalytic activity in the polymerization reaction of polyether carbonate polyol, and a method for producing the same.

[0006] In addition, one embodiment provides a method for producing high-quality polyether carbonate polyols using the double metal cyanide catalyst. [Means for solving the problem]

[0007] One aspect of the present invention provides a composition for double metal cyanide catalysts, comprising tert-butanol, a linear or cyclic (C2-C12) aliphatic polyhydric alcohol, and a polyalkylene glycol as complexing agents.

[0008] The complexing agent may contain tert-butanol and an aliphatic polyhydric alcohol in a molar ratio of 1:0.1 to 0.9.

[0009] The aliphatic polyhydric alcohol may be a diol or a triol.

[0010] The aliphatic polyhydric alcohol may be a 1,2-diol, a 1,3-diol or a 1,2,3-triol.

[0011] The aliphatic polyhydric alcohol may be one or more selected from ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 3-amino-1,2-propanediol, 1,2-cyclohexanediol, and 1,2-cyclopentadiol.

[0012] The double metal cyanide catalyst composition may include a metal salt of the following Chemical Formula 1 and a metal cyanide complex salt of the following Chemical Formula 2. [ka] [ka] (In the above Chemical Formulas 1 and 2, M 1 is a Group 11 or 12 transition metal ion, X 1 is a halogen, a hydroxy group, a sulfate group, a carbonate group, a carboxylate group, an oxalate group or a cyanide group, A 1 is an alkali metal ion or alkaline earth metal ion, M 2 and M 3 are different from each other and are alkaline earth metal ions or Group 8, 9, or 10 transition metal ions; p and q are each independently an integer of 1 or greater, and r is 0 or 1.

[0013] Said M 1 is Zn(II), Fe(II), Co(II) or Ni(II), and X 1 may be a halogen.

[0014] The metal salt may be zinc(II) chloride, zinc(III) chloride, zinc bromide or zinc iodide.

[0015] Said M 2 and M 3 may each independently be Ca(II), Co(II), Co(III), Fe(II), Fe(III), Cr(II), Ir(III), or Ni(II).

[0016] The metal cyanide complex may be potassium hexacyanocobaltate(III), potassium hexacyanoferrate(III) or potassium calcium ferrocyanide.

[0017] Yet another aspect of the present invention provides a double metal cyanide catalyst prepared from the double metal cyanide catalyst composition.

[0018] In yet another aspect, the present invention provides a method for producing a double metal cyanide catalyst, the method comprising: (a) preparing and reacting a composition for a double metal cyanide catalyst, the composition comprising tert-butanol, a linear or cyclic (C2-C12) aliphatic polyhydric alcohol, and a complexing agent comprising a polyalkylene glycol, a metal salt of the following Chemical Formula 1, and a metal cyanide complex salt of the following Chemical Formula 2; and (b) filtering and washing the composition to obtain the double metal cyanide catalyst. [ka] [ka] (In the above Chemical Formulas 1 and 2, X 1 , M 1 , M 2 , M 3 , A 1 , p to r are the same as defined above.)

[0019] Yet another aspect of the present invention provides a method for producing polyether carbonate polyol, comprising: (a) preparing and reacting a composition for a double metal cyanide catalyst, the composition comprising tert-butanol, a linear or cyclic (C2-C12) aliphatic polyhydric alcohol, a complexing agent comprising polyalkylene glycol, a metal salt represented by the following Chemical Formula 1, and a metal cyanide complex salt represented by the following Chemical Formula 2; (b) filtering and washing the resulting mixture to obtain a double metal cyanide catalyst; and (c) reacting an alkylene oxide with carbon dioxide in the presence of the double metal cyanide catalyst to obtain a polyether carbonate polyol. [ka] [ka] (In the above Chemical Formulas 1 and 2, X 1 , M 1, M 2 , M 3 , A 1 , p to r are the same as defined above.)

[0020] The polyether carbonate polyol may have a number average molecular weight of 200 to 10,000 g / mol.

[0021] In the step (c), the catalytic activity calculated based on the ratio of the weight of the produced polyol (kg-P) to the amount of the double metal cyanide catalyst used (g-cat) based on the polymerization time (h) may be 1 to 40 kg-P / g-cat.h. [Effects of the Invention]

[0022] In one embodiment, the double metal cyanide catalyst can achieve significantly improved catalytic activity by including tert-butanol and a linear or cyclic (C2-C12) aliphatic polyhydric alcohol as a complexing agent.

[0023] Specifically, when a double metal cyanide catalyst according to one embodiment is applied to a polyether carbonate polyol polymerization reaction, a high-quality polymer can be produced using only a very small amount of catalyst. Furthermore, since there is almost no catalyst residue after the polymerization reaction, an additional catalyst removal process is not required, simplifying the process. High-quality polyether carbonate polyol can be obtained even under mild reaction conditions, significantly improving productivity. DETAILED DESCRIPTION OF THE INVENTION

[0024] Unless otherwise defined herein, all technical and scientific terms have the same meaning as commonly understood by those skilled in the art to which this invention belongs. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0025] As used herein, the singular forms "a," "an," and "the" can be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0026] Furthermore, the numerical ranges used herein include the lower and upper limits, all values ​​within the range, increments logically derived from the shape and width of the defined range, all doubly limited values, and all possible combinations of upper and lower limits of numerical ranges limited in different ways. Unless otherwise specified in this specification, values ​​outside the numerical range that may occur due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0027] As used herein, the term "comprising" is an open-ended term having the same meaning as expressions such as "comprising," "containing," "having," or "characterized by," and does not exclude further unrecited elements, materials, or steps.

[0028] The present invention will be specifically described below.

[0029] One aspect of the present invention provides a double metal cyanide catalyst having excellent catalytic activity in the polymerization reaction of polyether carbonate polyol, and a method for producing the same.

[0030] Specifically, a composition for a double metal cyanide catalyst according to one embodiment is characterized by including tert-butanol, a linear or cyclic (C2-C12) aliphatic polyhydric alcohol, and a polyalkylene glycol as complexing agents.

[0031] By using the complexing agent in the above-described combination, a double metal cyanide catalyst according to one embodiment can produce high-quality polymers in a polyether carbonate polyol polymerization reaction even in very small amounts.

[0032] For example, the complexing agent may contain tert-butanol and an aliphatic polyhydric alcohol in a molar ratio of 1:0.1 to 0.9, more specifically, a molar ratio of 1:0.2 to 1:0.8, or a molar ratio of 1:0.2 to 1:0.6. When the above range is satisfied, a double metal cyanide catalyst with better catalytic activity can be produced, which is preferable, but is not necessarily limited thereto.

[0033] The linear or cyclic (C2-C12) aliphatic polyhydric alcohol may be, for example, a linear (C2-C12) aliphatic polyhydric alcohol or a cyclic (C3-C10) aliphatic polyhydric alcohol. Specifically, it may be a linear or cyclic (C3-C8) aliphatic polyhydric alcohol or a (C3-C6) aliphatic polyhydric alcohol, or may be a linear or cyclic aliphatic compound containing two or more, specifically 2 to 4, hydroxy groups (—OH).

[0034] The aliphatic polyhydric alcohol may be a diol or triol, and may be one or more selected from, but not limited to, ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 3-amino-1,2-propanediol, 1,2-cyclohexanediol, and 1,2-cyclopentadiol.

[0035] The aliphatic polyhydric alcohol may be a 1,2-diol, a 1,3-diol or a 1,2,3-triol, preferably a 1,2-diol.

[0036] Here, the 1,2-diol refers to a vicinal diol in which two hydroxy groups are located on adjacent carbon atoms, as shown in the following chemical formula A. Non-limiting examples include ethylene glycol, propylene glycol, 1,2-butanediol, 2,3-butanediol, 3-amino-1,2-propanediol, 1,2-cyclohexanediol, and 1,2-cyclopentanediol.

[0037] [ka]

[0038] The 1,3-diol refers to a compound in which two hydroxy groups are located at the 1st and 3rd carbon atoms, as shown in the following chemical formula B. Non-limiting examples include 1,3-propanediol and 1,3-butanediol.

[0039] [ka]

[0040] The 1,2,3-triol refers to a compound in which three hydroxy groups are located on three adjacent carbon atoms, as shown in the following chemical formula C, and a non-limiting example thereof is glycerol.

[0041] [ka]

[0042] The polyalkylene glycol may be a polymer compound having a number average molecular weight of 400 g / mol or more, specifically 400 to 5,000 g / mol, 400 to 3,000 g / mol, or 400 to 2,000 g / mol. The polyalkylene glycol may be, but is not limited to, polyethylene glycol, polypropylene glycol, or polybutylene glycol. Specifically, a double metal cyanide catalyst composition according to one embodiment may include the complexing agent, metal salt, and metal cyanide complex salt described above. The metal salt may be represented by the following Chemical Formula 1, and the metal cyanide complex salt may be represented by the following Chemical Formula 2:

[0043] [ka]

[0044] [ka]

[0045] (In the above Chemical Formulas 1 and 2, M 1 is a Group 11 or 12 transition metal ion, X 1 is a halogen, a hydroxy group, a sulfate group, a carbonate group, a carboxylate group, an oxalate group or a cyanide group, A 1 is an alkali metal ion or alkaline earth metal ion, M 2 and M 3 are different from each other and are alkaline earth metal ions or Group 8, 9, or 10 transition metal ions; p and q are each independently an integer of 1 or greater, and r is 0 or 1.

[0046] In the above chemical formula 1, p is M 1 is the same as the charge value of M 1 is Zn, Fe, Co or Ni, and X 1may be a halogen. Specifically, the metal salt represented by Chemical Formula 1 may be zinc chloride (II) (ZnCl), zinc chloride (III) (ZnCl), zinc bromide (ZnBr), or zinc iodide (ZnI), and more specifically, zinc chloride (II).

[0047] In the above formula 2, when r is 0, q is 6-(M 2 charge value), and when r is 1, q is 6-(M 2 Charge value of +M 3 charge value of M 2 and M 3 may each independently be Ca(II), Co(II), Co(III), Fe(II), Fe(III), Cr(II), Ir(III), or Ni(II); A 1 may be an alkali metal ion. Specifically, the metal cyanide complex salt represented by Chemical Formula 2 may be potassium hexacyanocobaltate(III) (KCo(CN)), potassium hexacyanoferrate(III) (KFe(CN)), or potassium calcium ferrocyanide (KCaFe(CN)), specifically potassium hexacyanocobaltate(III) (KCo(CN)) or potassium hexacyanoferrate(III) (KFe(CN)).

[0048] Yet another aspect of the present invention provides a method for preparing a double metal cyanide catalyst.

[0049] According to one embodiment, a method for producing a double cyanide catalyst includes: (a) preparing and reacting a double metal cyanide catalyst composition comprising a complexing agent including tert-butanol, a linear or cyclic (C2-C12) aliphatic polyhydric alcohol and a polyalkylene glycol, a metal salt of the following Chemical Formula 1, and a metal cyanide complex salt of the following Chemical Formula 2: (b) filtering and washing to obtain the double metal cyanide catalyst; may include:

[0050] [ka]

[0051] [ka]

[0052] (In the above chemical formulas 1 and 2, X 1 , M 1 , M 2 , M 3 , A 1 , p to r are as described above.)

[0053] The explanations regarding the linear or cyclic (C2-C12) aliphatic polyhydric alcohol, polyalkylene glycol, metal salt and metal cyanide complex salt are as described above and will be omitted here.

[0054] Specifically, the reaction in step (a) may be carried out at, for example, 30 to 100°C, or 30 to 80°C, or 40 to 60°C for 30 minutes to 2 hours, or 1 to 2 hours.

[0055] In step (b), an aqueous solution containing tert-butanol and polyalkylene glycol may be used as a washing solution. After washing, the solvent is removed by drying under reduced pressure to obtain the double metal cyanide catalyst. The drying may be performed at 50 to 100°C, 70 to 100°C, or 80 to 100°C for 1 to 10 hours, 3 to 10 hours, or 5 to 20 hours.

[0056] In yet another aspect, the present invention provides a double metal cyanide catalyst produced by the above-mentioned production method, and a method for producing a polyether carbonate polyol, comprising reacting an alkylene oxide with carbon dioxide in the presence of the double metal cyanide catalyst to obtain a polyether carbonate polyol.

[0057] Specifically, one embodiment of a method for producing a polyether carbonate polyol includes the steps of: (a) preparing and reacting an aqueous solution containing tert-butanol, a linear or cyclic (C2-C12) aliphatic polyalcohol, a complexing agent including a polyalkylene glycol, a metal salt represented by the following Chemical Formula 1, and a metal cyanide complex salt represented by the following Chemical Formula 2; (b) filtering and washing the solution to obtain a double metal cyanide catalyst; and (c) reacting an alkylene oxide with carbon dioxide in the presence of the double metal cyanide catalyst to obtain a polyether carbonate polyol.

[0058] [ka]

[0059] [ka]

[0060] (In the above chemical formulas 1 and 2, X 1 , M 1 , M 2 , M 3 , A 1 , p to r are as described above.)

[0061] The double metal cyanide catalyst according to one embodiment has such excellent catalytic activity that a catalyst removal step is not required. Specifically, the use of the double metal cyanide catalyst according to one embodiment allows the production of high-quality polyether carbonate polyols with only a very small amount of catalyst. Furthermore, since there is almost no catalyst residue after the polymerization reaction, an additional catalyst removal step is not required, simplifying the process and allowing the production of high-quality polyether carbonate polyols even under mild reaction conditions, thereby significantly improving productivity.

[0062] Specifically, in step (c), the double metal cyanide catalyst may be used in an amount of 400 ppm or less, or 300 ppm or less, or 200 ppm or less, or 100 ppm or less, or 50 ppm or less, based on the weight of the final produced polyether carbonate polyol, specifically 10 to 400 ppm, or 50 to 300 ppm, or 100 to 300 ppm, and all possible combinations of the upper and lower limits of the numerical ranges may be included.

[0063] Furthermore, the double metal cyanide catalyst may be used in an amount of 0.001 to 0.1 parts by weight, or 0.001 to 0.05 parts by weight, relative to 100 parts by weight of the alkylene oxide.

[0064] In the step (c), the alkylene oxide may be ethylene oxide or propylene oxide, and the reaction of the alkylene oxide with carbon dioxide may be carried out at 50 to 200°C, or 70 to 200°C, or 80 to 150°C.

[0065] In addition, step (c) may be carried out by further adding a chain transfer agent to the alkylene oxide and carbon dioxide. The chain transfer agent may be any agent commonly used in the art, but is not limited to these. A non-limiting example of the chain transfer agent is polyalkylene glycol, more specifically, polyethylene glycol, polypropylene glycol, or polybutylene glycol. The number average molecular weight of the polyalkylene glycol used as the chain transfer agent may be, but is not limited to, 50 to 2,000 g / mol, 50 to 1,000 g / mol, 100 to 1,000 g / mol, or 100 to 500 g / mol.

[0066] Under the above polymerization conditions, the catalytic activity calculated as the ratio of the weight of polyol produced (kg-P) to the amount of double metal cyanide catalyst used (g-cat) based on the polymerization time (h) may be 1 to 40 kg-P / g-cat.h, or 3 to 40 kg-P / g-cat.h.

[0067] The number average molecular weight of the polyether carbonate polyol obtained by the above production method may be, but is not necessarily limited to, 200 to 10,000 g / mol, or 200 to 5,000 g / mol, or 300 to 5,000 g / mol, or 400 to 3,000 g / mol.

[0068] The above-described embodiments will be described in more detail below with reference to examples, which are provided for illustrative purposes only and are not intended to limit the scope of the invention.

[0069] The physical properties of the examples were measured as follows.

[0070] 1) Molecular weight and dispersity Analysis was performed using gel permeation chromatography (GPC) on an Agilent 1260 Infinity II high temperature GPC instrument, with polystyrene as the standard, tetrahydrofuran as the solvent, and a PSS SDV 500A column at 40°C. o The test was performed under the conditions of 3 μm 8 × 300 mm from Agilent.

[0071] 2) Catalytic activity The catalytic activity was calculated as the ratio of the weight of polyether carbonate polyol (kg-P) produced to the amount of double metal cyanide catalyst (g-cat) used based on the polymerization time (h), expressed in units of kg-P / g-cat.h.

[0072] [Example 1] Preparation of double metal cyanide catalyst (DMC) The double metal cyanide catalyst of Example 1 was prepared using tertiary butyl alcohol and 2,3-butanediol as complexing agents in a 1:0.5 molar ratio.

[0073] Specifically, 6.5 g of ZnCl, 3.4 g of tertiary butyl alcohol, and 2.1 g of 2,3-butanediol were dissolved in 24.0 g of distilled water. In another reaction vessel, 0.65 g of KCo(CN) was dissolved in 8.0 g of distilled water, and this mixture was added dropwise to the ZnCl solution over 10 minutes with stirring. After the addition was complete, a mixture of 0.14 g of tertiary butyl alcohol and 0.69 g of polypropylene glycol (molecular weight 1000 g / mol) in 6.5 g of distilled water was added dropwise over 10 minutes to prepare a double metal cyanide catalyst composition. After the addition was complete, the mixture was allowed to react for an additional 90 minutes with stirring. The entire reaction was carried out at 50°C. The white slurry was then filtered to obtain a white solid product. The product was then dispersed in a mixed solvent of 15 g of distilled water, 29 g of tertiary butyl alcohol, and 0.6 g of polypropylene glycol (molecular weight 1,000 g / mol), washed with stirring for 20 minutes, and then filtered. This washing process was repeated twice. The white product was then dispersed in 40 g of tertiary butyl alcohol, stirred for 20 minutes, and then filtered to obtain a white product. The solvent was then removed under reduced pressure at 60°C for 8 hours to obtain the double metal cyanide catalyst of Example 1.

[0074] Manufacture of polyether carbonate polyols 6.0 mg of the DMC catalyst prepared in Example 1, 20 g of propylene oxide, and 50 g of polypropylene glycol (molecular weight 400 g / mol) as a chain transfer agent were placed in a 600 mL reactor and stirred. The reactor was heated to 110°C to polymerize propylene oxide. An internal temperature increase was observed, and the internal pressure subsequently decreased to 1 bar. The reactor was then cooled to room temperature. 150 g of propylene oxide was then placed in the reactor, and carbon dioxide gas was pressurized to 18 bar. The reactor was then heated to 115°C. The pressure inside the reactor was observed to decrease as the polymerization reaction proceeded, and the polymerization was completed when the pressure dropped to 35 bar. After completion of the reaction, the reactor was cooled using an ice bath, and all carbon dioxide gas inside the reactor was vented. The product was dried in a vacuum oven at 80°C. The physical properties of the product are shown in Table 1 below, and the CO2 content in the obtained polyether carbonate polyol was measured by the method described in Korean Patent Publication No. 10-2022-0111266A.

[0075] [Example 2] The same procedure was carried out as in Example 1, except that the total amounts of tertiary butyl alcohol and 2,3-butanediol used in preparing the DMC catalyst composition were the same, but the molar ratio was changed from 1:0.5 to 1:0.2.

[0076] [Example 3] The same procedure as in Example 1 was carried out, except that propylene glycol was used instead of 2,3-butanediol when preparing the DMC catalyst composition.

[0077] [Example 4] The same procedure as in Example 1 was carried out, except that 1,2-cyclohexanediol was used instead of 2,3-butanediol when preparing the DMC catalyst composition.

[0078] [Example 5] The same procedure was carried out as in Example 1, except that the total amounts of tertiary butyl alcohol and 2,3-butanediol used in preparing the DMC catalyst composition were the same, but the molar ratio was changed from 1:0.5 to 1:1.0.

[0079] [Example 6] The same procedure as in Example 1 was carried out, except that 1,3-propanediol was used instead of 2,3-butanediol when preparing the DMC catalyst composition.

[0080] [Example 7] The same procedure as in Example 1 was carried out, except that 3-amino-1,2-propanediol was used instead of 2,3-butanediol when preparing the DMC catalyst composition.

[0081] [Comparative Example 1] The same procedure as in Example 1 was carried out, except that 2,3-butanediol was not used in the preparation of the DMC catalyst composition.

[0082] [Table 1]

[0083] As shown in Table 1, the DMC catalysts according to the embodiments of the present invention exhibit significantly improved catalytic activity, making it possible to produce high-quality polymers even with very small amounts of catalyst. Furthermore, according to the embodiments of the present invention, the amount of catalyst residue is minimal (about 50 ppm or less) after the polymerization reaction, eliminating the need for a catalyst removal process and simplifying the process. Furthermore, high-quality polyether carbonate polyols can be obtained even under mild reaction conditions, which is expected to significantly improve productivity.

[0084] As described above, the present invention has been described using specific matters and limited examples, but this is provided to facilitate a more general understanding of the present disclosure, and the present invention is not limited to the above examples. A person having ordinary knowledge in the field to which the present invention belongs can make various modifications and variations from such descriptions.

[0085] Therefore, the concept of the present invention should not be limited to the above-described embodiments, and it can be said that not only the scope of the claims described below, but also all other equivalent or similar modifications to the scope of the claims fall within the scope of the concept of the present invention.

Claims

1. A composition for double metal cyanide catalysts comprising tert-butanol, a linear or cyclic (C2-C12) aliphatic polyhydric alcohol, and a polyalkylene glycol as complexing agents.

2. 2. The double metal cyanide catalyst composition of claim 1, wherein the complexing agent comprises tert-butanol and an aliphatic polyhydric alcohol in a molar ratio of 1:0.1-0.

9.

3. 2. The double metal cyanide catalyst composition of claim 1, wherein the aliphatic polyhydric alcohol is a diol or triol.

4. 4. The double metal cyanide catalyst composition of claim 3, wherein the aliphatic polyhydric alcohol is a 1,2-diol, a 1,3-diol, or a 1,2,3-triol.

5. 5. The double metal cyanide catalyst composition of claim 4, wherein the aliphatic polyhydric alcohol is one or more selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 3-amino-1,2-propanediol, 1,2-cyclohexanediol, and 1,2-cyclopentadiol.

6. 2. The double metal cyanide catalyst composition of claim 1, comprising a metal salt of the following formula 1 and a metal cyanide complex salt of the following formula 2: 【Chemistry 16】 【Chemistry 17】 In the above Chemical Formulas 1 and 2, M １ is a Group 11 or 12 transition metal ion, X １ is a halogen, a hydroxy group, a sulfate group, a carbonate group, a carboxylate group, an oxalate group or a cyanide group, A １ is an alkali metal ion or alkaline earth metal ion, M ２ and M ３ are different from each other and are alkaline earth metal ions or Group 8, 9, or 10 transition metal ions; p and q each independently represent an integer of 1 or more; r is 0 or 1;

7. Said M １ is Zn(II), Fe(II), Co(II) or Ni(II), and X １ 7. The double metal cyanide catalyst composition of claim 6, wherein is a halogen.

8. 7. The double metal cyanide catalyst composition of claim 6, wherein the metal salt is zinc chloride (II), zinc chloride (III), zinc bromide, or zinc iodide.

9. Said M ２ and M ３ is each independently Ca(II), Co(II), Co(III), Fe(II), Fe(III), Cr(II), Ir(III), or Ni(II).

10. 7. The double metal cyanide catalyst composition of claim 6, wherein the metal cyanide complex salt is potassium hexacyanocobaltate(III), potassium hexacyanoferrate(III), or potassium calcium ferrocyanide.

11. A double metal cyanide catalyst produced from the double metal cyanide catalyst composition according to any one of claims 1 to 10.

12. (a) preparing and reacting a double metal cyanide catalyst composition comprising tert-butanol, a complexing agent comprising a linear or cyclic (C2-C12) aliphatic polyhydric alcohol and a polyalkylene glycol, a metal salt of the following Chemical Formula 1, and a metal cyanide complex salt of the following Chemical Formula 2: (b) filtering and washing to obtain the double metal cyanide catalyst. [Chemistry 18] 【Chemistry 19】 In the above Chemical Formulas 1 and 2, X １ , M １ , M ２ , M ３ , A １ , p to r are defined as in claim 6.

13. (a) preparing and reacting a double metal cyanide catalyst composition comprising tert-butanol, a complexing agent comprising a linear or cyclic (C2-C12) aliphatic polyhydric alcohol and a polyalkylene glycol, a metal salt of the following Chemical Formula 1, and a metal cyanide complex salt of the following Chemical Formula 2: (b) filtering and washing to obtain the double metal cyanide catalyst; (c) reacting an alkylene oxide with carbon dioxide in the presence of the double metal cyanide catalyst to obtain a polyether carbonate polyol. 【Chemistry 20】 【Chemistry 21】 In the above Chemical Formulas 1 and 2, X １ , M １ , M ２ , M ３ , A １ , p to r are defined as in claim 6.

14. The method for producing a polyether carbonate polyol according to claim 13, wherein the number average molecular weight of the polyether carbonate polyol is 200 to 10,000 g / mol.

15. 14. The method for producing polyether carbonate polyol according to claim 13, wherein in step (c), the catalyst activity calculated as the ratio of the weight of the produced polyol (kg-P) to the amount of the double metal cyanide catalyst used (g-cat) based on the polymerization time (h) is 1 to 40 kg-P / g-cat.h.

Images