Double metal cyanide catalyst, method of producing same, and polyol production method using same

Abstract

A double metal cyanide catalyst, according to an embodiment of the present invention, comprises a metal salt, a metal cyanide salt, a complexing agent, and a co-complexing agent, wherein the complexing agent includes at least one selected from acrylic or methacrylic compounds, and the co-complexing agent may be a homopolymer having a weight-average molecular weight of 5500 g / mol or less.

Description

Double metal cyanide catalyst and preparation method, and polyol preparation method using the same

[0001] The present invention relates to a double metal cyanide catalyst for producing polyols, a production method therefor, and a polyol production method therefor, and more particularly, to a double metal cyanide catalyst for producing polyols having high selectivity for polyols, a production method therefor, and a polyol production method therefor.

[0002]

[0003] Polyols are industrially mass-produced raw materials, typically in the form of polyether polyols, and are used as starting materials for polyurethane production together with polyisocyanates. Catalysts used in polyol production are generally soluble basic metal hydroxides, with potassium hydroxide (KOH) being the most commonly used. However, the use of alkali metal hydroxides increases the content of monofunctional polyethers with terminal double bonds, so-called monols, which is very disadvantageous for polyurethane production. On the other hand, the use of double metal cyanide (DMC) catalysts can not only relatively reduce the content of monols, but also increase the addition reaction rate of cyclohexene oxide (CHO) and propylene oxide (PO), and the polyether polyols thus obtained can be processed into advanced polyurethanes (e.g., coatings, elastomers, sealants, foams, and adhesives).

[0004] Meanwhile, recently, polyether carbonate polyol or polyol, which is a copolymer polyol with added CO2 as a high value-added compound through direct utilization of carbon dioxide (CO2), can also be used as a raw material for polyurethane. Co-polymerization using a DMC catalyst in a CO2 pressurized atmosphere is possible together with propylene oxide (PO) and glycol (or a polymerized form of polyethylene or polypropylene glycol), which are reactants used in the production of the polyether polyol (see the chemical formula below).

[0005]

[0006] Although many conventional technologies have been reported for DMC catalysts and manufacturing methods used in the production of polyether carbonate polyols as described above, a highly active catalyst is still required because it enables polymerization with only a small amount of catalyst during ring-opening polymerization, thereby omitting the catalyst removal process after polyol production. In other words, even with a small amount of input, it is required to increase the molecular weight and improve the reactivity of CO2, a thermodynamically stable substance, to be incorporated into the main chain in the form of carbonate. In addition, the polydispersity index (PDI), which indicates dispersibility, inevitably increases due to the random copolymerization of monomer PO and CO2 during the copolymerization of CO2 compared to the form of polyether polyol. This phenomenon needs to be controlled so that it is at the level of conventional polypropylene glycol or polyether polyol (PDI: <1.2), and the control of the terminal functional groups of the final polyol product is also a necessary factor for use as an advanced polyurethane material.

[0007] The main factors controlling the activity of DMC catalysts are the types and combinations of bimetals, complexing agents (CA), and co-complexing agents (co-CA), and their appropriate ratios and synthesis conditions (synthesis temperature, time, mixing order, drying method, etc.) have been proposed in prior art.

[0008] It is known that polymers synthesized using complexing agents such as alcohols, aldehydes, ketones, ethers, esters, amides, ureas, and nitriles, including conventional tert-butyl alcohol, have excellent polymerization degrees and physical properties. However, the demand for high CO2 content, dispersibility, and polyol selectivity still persists, and research is being conducted to develop highly efficient catalysts until recently.

[0009] Therefore, there is a need to develop a method for producing polyether carbonate polyol having excellent polyol selectivity, high CO2 content, and low PDI.

[0010]

[0011] One object of the present invention is to provide a double metal cyanide catalyst with high selectivity for polyether carbonate polyol and a method for producing the same.

[0012] Another object of the present invention is to provide a method for producing polyether carbonate polyol having a high CO2 content and low PDI using the above catalyst.

[0013]

[0014] A double metal cyanide catalyst according to one embodiment of the present invention comprises a metal salt; a metal cyanide salt, a complexing agent, and a co-complexing agent, wherein the co-complexing agent may be a homopolymer having a weight average molecular weight of 5500 g / mol or less.

[0015] The complexing agent may include at least one selected from among polyacrylic acid polymers, polyethylene glycol, polypropylene glycol, copolymers or mixtures thereof, and the complexing agent may include at least one selected from among acrylic or methacrylic compounds.

[0016] The above acrylic or methacrylic compound may include at least one selected from the following chemical compounds 1-1 to 1-2.

[0017] [Chemical Formula 1-1]

[0018]

[0019] [Chemical Formula 1-2]

[0020]

[0021] The above double metal cyanide catalyst may be a compound represented by the following chemical formula 1.

[0022] [Chemical Formula 1]

[0023] M a [M' (CN)6)] b ·L c ·L' d

[0024] In the above chemical formula 1, M is one selected from zinc (II), iron (II), iron (III), nickel (II), manganese (II), cobalt (II), tin (II), lead (II), molybdenum (IV), molybdenum (VI), aluminum (III), vanadium (V), vanadium (IV), strontium (II), tungsten (IV), tungsten (VI), copper (II), and chromium (III), M' is one selected from iron (II), iron (III), cobalt (II), cobalt (III), chromium (II), chromium (III), manganese (II), manganese (III), iridium (III), nickel (II), rhodium (III), ruthenium (II), vanadium (V), and vanadium (IV), L is a complexing agent including an acrylic or methacrylic compound, and L' is a hydrophilic complexing agent. Contains homopolymer, and a, b, c and d are positive.

[0025] The apparent density of the above double metal cyanide catalyst is 0.30 g / cm 3 0.60g / cm 3 It could be.

[0026] The above double metal cyanide catalyst may be a secondary particle in which layered nanosheets are laminated, and the average major axis length of the wide surface of the layered nanosheets may be 1.0 μm to 15.0 μm.

[0027] The average short axis length of the wide surface of the above layered nanosheet may be in the range of 1 / 7 to 6 / 7 of the average long axis length, and the average thickness of the nanosheet may be in the range of 25 nm to 85 nm.

[0028] According to another embodiment of the present invention, a method for producing a double metal cyanide catalyst may include the steps of: preparing a first solution containing a metal salt, a complexing agent, and water; preparing a second solution containing a metal cyanate salt and water; preparing a third solution containing a complexing agent and a co-complexing agent; preparing a fourth solution by mixing the first and second solutions; a first reaction step of adding the third solution to the fourth solution and reacting; a second reaction step of separating a precipitate formed in the first reaction step and then mixing the separated precipitate with a solution containing water and a complexing agent and reacting; a third reaction step of adding a fifth solution containing a complexing agent and a co-complexing agent and reacting after completion of the second reaction step; and a step of separating the precipitate formed in the third reaction step.

[0029] The above complexing agent may be a homopolymer having a weight average molecular weight of 5500 g / mol or less.

[0030] In the step of preparing a first solution containing the metal salt, complexing agent and water, the metal salt, complexing agent and water may be mixed and heated to a temperature of 50°C to 90°C.

[0031] In the step of preparing a second solution containing the metal cyanide and water, the metal cyanide and water can be mixed and heated to a temperature of 50°C to 70°C.

[0032] In the step of preparing a first solution containing the metal salt, complexing agent, and water, 0.04 mol to 1.0 mol of the complexing agent can be mixed per 1.0 mol of the water.

[0033] In the step of preparing the third solution including the complexing agent and the co-complexing agent, the molar ratio of the complexing agent to the co-complexing agent (complexing agent:co-complexing agent) may be 600:1 to 1200:1.

[0034] After the completion of the second reaction step, in the third reaction step of adding a fifth solution containing a complexing agent and a co-complexing agent to perform a reaction, the molar ratio of the complexing agent to the co-complexing agent in the fifth solution (complexing agent:co-complexing agent) may be 150:1 to 1250:1.

[0035] In the step of preparing a fourth solution by mixing the first solution and the second solution, the molar ratio of the metal cyanide to the metal salt in the prepared fourth solution (metal cyanide:metal salt) may be 2:1 to 30:1.

[0036] The above second reaction step and third reaction step can be performed two or more times.

[0037] The step of separating the precipitate formed in the third reaction step may further include a step of washing and drying the separated precipitate, and the step of washing and drying the separated precipitate may be performed by washing the precipitate using water.

[0038] Another embodiment of the present invention provides a method for producing a polyol, comprising the steps of: introducing the double metal cyanide catalyst and a solvent into a reactor; purging the inside of the reactor using CO2 gas; and then heating the reactor while controlling the pressure with CO2 gas.

[0039] The method may include a step of forming a product by introducing an initiator and an epoxy compound into the reactor; and a step of separating a polyol within the product.

[0040] The above initiator may be a compound represented by the following chemical formula 2.

[0041] [Chemical Formula 2]

[0042]

[0043] (In chemical formula 2, R is H or an alkyl group having 1 carbon atom, and n is an integer within the range of 1 to 227.)

[0044] The above epoxy compound may be a compound represented by the following chemical formula 3.

[0045] [Chemical Formula 3]

[0046]

[0047] (In Chemical Formula 3, R can be selected from H, -CH3, -CH3OH, methyl halide (-CH3F, -CH3Cl, -CH3Br), and an alkyl group having 1 to 8 carbon atoms.)

[0048] The weight average molecular weight of the polyol may be 3000 g / mol to 5000 g / mol, the polydispersity index (PDI) of the polyol may be 1.65 or less, and the number of functional groups of the polyol may be 2.5 or more.

[0049] The selectivity of the above polyol may be 65% or more.

[0050]

[0051] A catalyst according to one embodiment of the present invention has high selectivity for polyether carbonate polyol, and can produce polyether carbonate polyol having a high CO2 content and low PDI using the catalyst.

[0052]

[0053] Figure 1 shows the major and minor axes of an FE-SEM analysis image of a double metal cyanide catalyst according to one embodiment of the present invention.

[0054] Figure 2 shows scanning electron microscope (FE-SEM) analysis images of catalysts manufactured according to Manufacturing Examples 1, 3, and 4.

[0055]

[0056] The terms first, second, and third, etc., are used to describe, but are not limited to, various parts, components, regions, layers, and / or sections. These terms are used only to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Accordingly, a first part, component, region, layer, or section described below may be referred to as a second part, component, region, layer, or section without departing from the scope of the present invention.

[0057] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the present invention. As used herein, the singular forms "singular" and "comprising" include plural forms as well, unless the context clearly dictates otherwise. The word "comprising" as used herein specifies a particular feature, region, integer, step, operation, element, and / or component, but does not exclude the presence or addition of other features, regions, integers, steps, operations, elements, and / or components.

[0058] When a part is referred to as being "on" or "over" another part, it can be directly on or over the other part, or there may be other parts intervening. Conversely, when a part is referred to as being "directly on" another part, there are no other parts intervening.

[0059] Although not defined otherwise, all terms, including technical and scientific terms, used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention pertains. Terms defined in commonly used dictionaries are further interpreted to have meanings consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or overly formal unless otherwise defined.

[0060] Also, unless otherwise stated, % means weight%, and 1 ppm is 0.0001 weight%.

[0061] In this specification, the term "combination(s) thereof" described in the expression in the Makushi format means one or more mixtures or combinations selected from the group consisting of the components described in the expression in the Makushi format, and means including any one or more selected from the group consisting of said components.

[0062] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0063]

[0064] (double metal cyanide catalyst)

[0065] In one embodiment of the present invention, the double metal cyanide catalyst may include a metal salt; a metal cyanide, a complexing agent, and a co-complexing agent.

[0066]

[0067] The complexing agent and co-complexing agent included in the catalyst of the present invention can be used to increase the surface area and activity of the catalyst by changing the catalyst crystal size and crystallinity.

[0068] The complexing agent may include at least one selected from acrylic or methacrylic compounds, and the complexing agent may be a homopolymer.

[0069] The above acrylic or methacrylic compound may be selected from the following chemical formulas.

[0070] [Chemical Formula 1-1]

[0071]

[0072] [Chemical Formula 1-2]

[0073]

[0074] In one embodiment of the present invention, by using the acrylic or methacrylic compound as a complexing agent, the attraction between the complexing agent and the metal is appropriately controlled, and the complexing agent is appropriately coordinated within the catalyst matrix structure, so that high catalytic activity can be exhibited during polyol production.

[0075] In one embodiment of the present invention, the complexing agent may include at least one selected from among polyethylene glycol, polypropylene glycol, and poly(oxyethylene-block-propylene) copolymer, poly(oxyethylene-block-oxypropylene-block-oxyethylene) or polyacrylic acid polymer, and poly(ethylene-block-acrylic acid) copolymer, and specifically, may include at least one selected from among polyacrylic acid polymer, polyethylene glycol, polypropylene glycol, or copolymers or mixtures thereof.

[0076] The above complexing agent may include at least one selected from the following chemical formulas 1-3 or 1-4.

[0077] [Chemical Formula 1-3]

[0078]

[0079]

[0080] [Chemical Formula 1-4]

[0081]

[0082]

[0083] More specifically, the complexing agent may be a homopolymer. The weight average molecular weight of the homopolymer may be 6000 g / mol or less, specifically 5500 g / mol or less, and more specifically 5100 g / mol or less. The lower limit of the weight average molecular weight of the complexing agent is not particularly limited, but may be 500 g / mol or more, specifically 1000 g / mol or more.

[0084] If the weight average molecular weight of the complexing agent exceeds the above range, exposure of the catalytic active site becomes difficult during the polyol manufacturing reaction, which may result in a decrease in polymerization performance. If the weight average molecular weight is less than the above range, if the structure formation through interaction with the catalytic metal active site is not properly achieved, the structural stability of the metal catalyst may be lowered due to exposure to external air and moisture, which is not desirable.

[0085] Meanwhile, in one embodiment of the present invention, the metal salt constituting the double metal cyanide catalyst and the metal ion of the metal cyanide are any one selected from zinc (II), iron (II), iron (III), nickel (II), manganese (II), cobalt (II), tin (II), lead (II), molybdenum (IV), molybdenum (VI), aluminum (III), vanadium (V), vanadium (IV), strontium (II), tungsten (IV), tungsten (VI), copper (II), and chromium (III), and the metal ion of the metal cyanide may include, but is not limited to, one or more selected from iron (II), iron (III), cobalt (II), cobalt (III), chromium (II), chromium (III), manganese (II), manganese (III), iridium (III), nickel (II), rhodium (III), ruthenium (II), vanadium (V), and vanadium (IV).

[0086]

[0087] In one embodiment of the present invention, the double metal cyanide catalyst may be a compound represented by the following chemical formula 1.

[0088] [Chemical Formula 1]

[0089] M a [M' (CN)6)] b ·L c ·L' d

[0090] In the above chemical formula 1,

[0091] M is one selected from zinc (II), iron (II), iron (III), nickel (II), manganese (II), cobalt (II), tin (II), lead (II), molybdenum (IV), molybdenum (VI), aluminum (III), vanadium (V), vanadium (IV), strontium (II), tungsten (IV), tungsten (VI), copper (II), and chromium (III).

[0092] M' is one selected from iron (II), iron (III), cobalt (II), cobalt (III), chromium (II), chromium (III), manganese (II), manganese (III), iridium (III), nickel (II), rhodium (III), ruthenium (II), vanadium (V), and vanadium (IV).

[0093] L contains an acrylic or methacrylic compound as a complexing agent,

[0094] L' contains a hydrophilic homopolymer as a complexing agent,

[0095] a, b, c and d are positive integers.

[0096]

[0097] Figure 1 shows the major and minor axes of an FE-SEM analysis image of a double metal cyanide catalyst according to one embodiment of the present invention.

[0098] Referring to FIG. 1, a double metal cyanide catalyst according to one embodiment of the present invention may have a secondary particle shape formed by stacking nanosheets.

[0099] The wide surface of the above nanosheet (a1, a2) may have a polygonal shape, and specifically, may have a hexagonal shape.

[0100] The above nanosheet (a1, a2) may have a 2D layered shape and the average major axis length (L) of the wide surface may be 0.1 µm to 15.0 µm, specifically 0.5 µm to 15.0 µm, and more specifically 1.0 µm to 15.0 µm.

[0101] In the present invention, the major axis length (L) refers to the longest length on the wide surface of the nanosheet, and the minor axis length (W) may be in the range of 1 / 7 to 6 / 7 of the major axis length (L), specifically in the range of 1 / 6 to 5 / 6, and more specifically in the range of 1 / 5 to 4 / 5. The minor axis refers to the longest length among the lengths perpendicular to the major axis on the wide surface of the nanosheet.

[0102] In addition, the average thickness of the nanosheets (a1, a2) may be 10 nm to 100 nm, specifically 25 nm to 85 nm, more specifically 30 nm to 70 nm, and even more specifically 30 nm to 50 nm.

[0103] When the average major axis length (L), average minor axis length (W), and average thickness of the nanosheets satisfy the above ranges, by reducing the crystal thickness of the catalyst, a space is formed between the crystals, thereby increasing the number of exposed catalytic active sites. Accordingly, the rate (ratio) at which reactants are initiated at the active sites increases, thereby increasing the molecular weight during polyol synthesis, and since immediate polymerization occurs after the reactants are initiated, the probability of intermediates being formed as byproducts is reduced, thereby improving polymer selectivity, which is desirable.

[0104]

[0105] In the present invention, the average major axis length (L), average minor axis length (W) and average thickness of the nanosheets are calculated as average values ​​by measuring the major axis length, minor axis length and thickness of 10 to 30 secondary particles, 2 to 5 nanosheets per particle, observed in field emission scanning electron microscope (FE-SEM) analysis.

[0106] The above secondary particles can be specifically stacked such that adjacent nanosheets (a1, a2) are positioned with their wide surfaces facing each other. The average major axis length (L) of the above secondary particles based on the wide surface of the nanosheet can be 0.5 µm to 10.0 µm, and more specifically, 1.0 µm to 10.0 µm.

[0107] The above secondary particles may have an average short axis length (W) based on the wide surface of the nanosheet in the range of 1 / 7 to 6 / 7 of the average long axis length (L), specifically in the range of 1 / 6 to 5 / 6, and more specifically in the range of 1 / 5 to 4 / 5.

[0108] Meanwhile, the apparent density of the double metal cyanide catalyst composed of the above secondary particles is 0.30 g / cm 3 0.60g / cm 3 It can be, and specifically the apparent density is 0.35g / cm 3 0.45g / cm 3 It could be.

[0109] When the double metal cyanide catalyst satisfies the above range, if the crystal size or thickness is small and the particles are formed, clusters of small crystals are formed, which is preferable because the polymer molecular weight, selectivity, and uniformity can be improved due to the improved contact efficiency between the main reactants (PO, CO2, initiator) and the catalyst active site.

[0110]

[0111] (Method for producing a double metal cyanide catalyst)

[0112] Hereinafter, a method for producing a double metal cyanide catalyst according to another embodiment of the present invention will be described.

[0113] First, a first solution containing a metal salt, a complexing agent, and water; a second solution containing a metal cyanide salt and water; and a third solution containing a complexing agent and a co-complexing agent can be prepared.

[0114] The first solution containing the metal salt, complexing agent, and water can be heated to a temperature of 50°C to 90°C under stirring conditions after adding the metal salt, complexing agent, and water to a mixing container, and specifically, can be heated to a temperature of 50°C to 70°C. At this time, the stirring time can be 10 minutes or more, specifically, 10 minutes to 60 minutes, and more specifically, 15 minutes to 30 minutes. At this time, 0.04 mol to 1.0 mol of the complexing agent can be mixed per 1.0 mol of the water, specifically, 0.04 mol to 0.1 mol can be mixed.

[0115]

[0116] The second solution containing the metal cyanide and water can be heated to a temperature of 50°C to 90°C under stirring conditions after adding the metal cyanide and water to a mixing container, and specifically, can be heated to a temperature of 50°C to 70°C. At this time, the stirring time can be 30 minutes or more, and specifically, can be 30 minutes to 90 minutes.

[0117] The third solution containing the complexing agent and the co-complexing agent can be prepared by adding the complexing agent and the co-complexing agent to a mixing vessel and stirring at room temperature. At this time, the molar ratio of the complexing agent to the co-complexing agent (complexing agent:co-complexing agent) can be 200:1 to 1200:1, and specifically, 600:1 to 1200:1.

[0118] When preparing the first solution, the second solution, and the third solution under the above conditions, it is preferable that the metal salt and complexing agent are uniformly dispersed in water to form a precipitate.

[0119] In addition, the first solution and the second solution prepared above are mixed to prepare a fourth solution. Specifically, the first solution and the second solution are mixed under room temperature conditions and stirred uniformly to prepare the fourth solution. At this time, the molar ratio of the metal cyanide to the metal salt in the prepared fourth solution (metal cyanide:metal salt) may be 2:1 to 30:1, specifically 2:1 to 25:1, and more specifically 2:1 to 10:1. If the molar ratio of the metal cyanide to the metal salt exceeds the above range, unreacted metal is included in the prepared catalyst, thereby lowering the catalytic activity, and if it is less than the above range, the amount of metal having an active site is minimal, thereby lowering the catalytic activity.

[0120] Next, a first reaction step can be performed by adding the third solution to the fourth solution thus prepared. Specifically, the reaction can be carried out under stirring conditions for 1 to 20 minutes, and more specifically, for 1 to 10 minutes. By carrying out the reaction under the above conditions, the desired catalyst can be economically produced.

[0121] After completing the first reaction step, the precipitate formed in the first reaction step may be separated, and then a second reaction step may be performed in which the separated precipitate is mixed with a solution containing water and a complexing agent and reacted. In one embodiment of the present invention, the second reaction step may be performed under conditions of heating to a temperature of 50°C to 90°C while mixing using a stirrer, and specifically, may be performed under conditions of heating to a temperature of 50°C to 70°C for about 60 minutes.

[0122] After the completion of the second reaction step, a third reaction step is performed by adding a fifth solution containing a complexing agent and a co-complexing agent, and the precipitate formed in the third reaction step can be separated using a centrifuge. The molar ratio of the complexing agent to the co-complexing agent in the fifth solution (complexing agent:co-complexing agent) can be 150:1 to 1250:1.

[0123] The precipitate separated in the third reaction step can be washed with distilled water and then dried to obtain the final product, a double metal cyanide catalyst.

[0124] Meanwhile, in one embodiment of the present invention, the second reaction step and the third reaction step may be performed repeatedly two or more times.

[0125] The separated precipitate may be subjected to a fourth reaction step, wherein the separated precipitate is mixed with a solution containing water and a complexing agent to undergo a reaction. At this time, the concentration of the complexing agent in the solution containing water and a complexing agent in the fourth reaction step may be equal to or less than the concentration of the complexing agent in the solution containing water and a complexing agent in the second reaction step. Meanwhile, the reaction temperature and reaction time of the fourth reaction step may be the same as those of the second reaction step.

[0126] Meanwhile, after the completion of the fourth reaction step, a fifth reaction step may be performed by adding a mixed solution containing a complexing agent and a co-complexing agent to cause a reaction. At this time, the molar ratio of the complexing agent and the co-complexing agent in the mixed solution containing the complexing agent and the co-complexing agent added in the fourth reaction step may be equal to or less than the molar ratio of the complexing agent to the co-complexing agent in the fifth solution (complexing agent:co-complexing agent).

[0127] In the fifth reaction step, the precipitate separated was separated into a solid precipitate using centrifugation, washed with 100 mL of distilled water, and centrifuged three times to obtain a final solid precipitate. The final catalyst precipitate was dried at 80°C and under a vacuum of 30 in.Hg until a constant weight was obtained, thereby obtaining the final product, a double metal cyanide catalyst.

[0128] Metal salts, metal cyanides, complexing agents and co-complexing agents have been described above and are therefore omitted here.

[0129]

[0130] (Method for producing polyol)

[0131] Another embodiment of the present invention provides a method for producing a polyol.

[0132] Specifically, a method for producing a polyol by polymerizing an epoxy compound in the presence of the above-described double metal cyanide catalyst and initiator is provided.

[0133] First, the above-mentioned double metal cyanide catalyst and solvent are introduced into the reactor. Here, the solvent may be an organic solvent, and specifically, may be at least one selected from toluene, hexane, and chloroform.

[0134] Next, the interior of the reactor is purged with CO2 gas to form a CO2 atmosphere, the reactor is sealed, and then the reactor is heated. Meanwhile, the internal pressure of the reactor can be controlled by adjusting the amount of CO2 supplied.

[0135] Next, a step of forming a product by introducing an initiator and an epoxy compound into the reactor can be performed.

[0136] The double metal cyanide catalyst and solvent loaded into the above reactor are stirred while adding an initiator and an epoxy compound, and the reaction can be carried out for 2 hours. At this time, the reactor temperature can be 100°C or higher, the reaction pressure can be 15 barg or higher, and the reaction time can be approximately 2 hours.

[0137] Meanwhile, the initiator may be a compound represented by the following chemical formula 2.

[0138] [Chemical Formula 2]

[0139]

[0140] In the above chemical formula 2, R is H or an alkyl group having 1 carbon atom, and n is an integer within the range of 1 to 227.

[0141] The above epoxy compound may be a compound represented by the following chemical formula 3.

[0142] [Chemical Formula 3]

[0143]

[0144]

[0145] In the above chemical formula 3, R can be selected from H, -CH3, -CH3OH, methyl halide (-CH3F, -CH3Cl, -CH3Br), and an alkyl group having 1 to 8 carbon atoms.

[0146] After the step of forming a product by introducing the above initiator and epoxy compound into the reactor is completed, the catalyst is separated through filtration. The solvent from which the catalyst has been separated can be vacuum evaporated to remove unreacted epoxy compounds, thereby producing a polyether carbonate polyol. At this time, propylene carbonate (PC), a byproduct, may be included.

[0147] Liquid-liquid separation can be performed to obtain the final product, polyol.

[0148] The weight average molecular weight of the polyol manufactured according to the method for manufacturing the polyol of the present invention may be 3000 g / mol or more, specifically 3150 g / mol to 5000 g / mol, and more specifically 3200 g / mol to 4000 g / mol.

[0149] The polydispersity index (PDI) of the polyol manufactured according to the method for manufacturing the polyol of the present invention may be 1.65 or less, specifically 1.60 or less, and more specifically 1.45 or less.

[0150] The functional group number of the polyol manufactured according to the method for manufacturing the polyol of the present invention may be 2.5 or more, and specifically, 2.7 or more.

[0151] The selectivity of the polyol manufactured according to the method for manufacturing the polyol of the present invention may be 65% or more.

[0152] A polyol having the above characteristics is preferable as a polyol product used in the manufacture of polyurethane foam, film, and coatings because it can form an appropriate molecular weight, polydispersity index, and number of functional groups.

[0153] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples, and the present invention is not limited thereby, and the present invention is defined only by the scope of the claims set forth below.

[0154]

[0155] Manufacturing Example 1: Manufacturing of double metal cyanide catalyst DMC-AA-P123

[0156] Solution 1 was prepared by mixing 36 g of zinc chloride, 138 g of distilled water, and 24.5 g of the complexing agent, Acrylic acid (AA), in the first beaker. Solution 2 was prepared by dissolving 3.9 g of potassium hexacyanocobaltate in 16 mL of distilled water in the second beaker. Solution 3 was prepared by dissolving 2.9 g of the complexing agent, poly(ethylene glycol)-Block-Poly(propylene glycol)-Block-poly(ethylene glycol) (Pluronic 123; P-123, Mn=5,800 g / mol), in 22.1 g of AA in the third beaker. After pouring solution 1 into a spherical flask, the mixture was stirred at 50°C using a mechanical stirrer, and solution 2 was added and reacted for 1 hour. Then, solution 3 was added and reacted for 5 minutes. After the reaction, the solution was separated using a high-speed centrifuge to obtain a solid precipitate. To the precipitate, 60 g of distilled water and 22.1 g of AA were added, and the mixture was reacted at 50 °C for 1 hour while mixing using a mechanical stirrer. After 1 hour of reaction, a mixed solution of 1.46 g of P-123 dissolved in 22.1 g of AA was added, and the mixture was stirred for 5 minutes. After the reaction, the solid was separated again using a high-speed centrifuge, and to the obtained precipitate, 60 g of distilled water and 11 g of AA were added, and the mixture was reacted at 50 °C for 1 hour while mixing using a mechanical stirrer. After 1 hour of reaction, a mixed solution of 6 g of P-123 dissolved in 14.7 g of AA was added, and the mixture was stirred for 5 minutes. The solid precipitate obtained using centrifugation was separated, washed with 100 mL of distilled water, and centrifuged three times to obtain the final solid precipitate. The final catalyst precipitate was dried at 80°C under 30 in.Hg vacuum until constant weight was obtained, thereby preparing the double metal cyanide catalyst DMC-AA-P123.

[0157] The apparent density of the catalyst DMC-AA-P123 manufactured at this time was 0.6904 g / cm 3 am.

[0158] The above apparent density measurement was calculated by placing 0.5 g of dried catalyst powder in a 1 ml graduated cylinder, checking the volume (ml) on the scale, and measuring the weight (g) using a precision balance.

[0159] Density = mass (g) / volume (ml)

[0160]

[0161] Manufacturing Example 2: Manufacturing of double metal cyanide catalyst DMC-AA-PAA

[0162] A catalyst was prepared in the same manner as in Manufacturing Example 1, except that the complexing agent Poly(acrylic acid sodium salt)(PAA, Mw ~5,100 g / mol) (Homo-polymer) was used instead of the complexing agent P-123 (Co-polymer). The amount of PAA used was the same molar ratio as P-123 and varied by the difference in molecular weight, and finally, a double metal cyanide catalyst DMC-AA-PAA catalyst was prepared.

[0163] The apparent density of the catalyst DMC-AA-PAA manufactured at this time was 0.4352 g / cm 3 am.

[0164]

[0165] Manufacturing Example 3: Manufacturing of double metal cyanide catalyst DMC-MA-PAA

[0166] A catalyst was prepared in the same manner as in Manufacturing Example 2, except that the complexing agent methacrylic acid (MA) was used instead of the complexing agent acrylic acid (AA). The amount of MA used was the same molar ratio as AA and varied by the difference in molecular weight, and finally a double metal cyanide catalyst DMC-MA-PAA catalyst was prepared.

[0167] The apparent density of the catalyst DMC-MA-PAA manufactured at this time was 0.3640 g / cm 3 am.

[0168]

[0169] Manufacturing Example 4: Manufacturing of double metal cyanide catalyst DMC-MA

[0170] A double metal cyanide catalyst DMC-MA catalyst was prepared in the same manner as in Manufacturing Example 3, except that the complexing agent PAA was not used.

[0171] The apparent density of the catalyst DMC-MA-PAA manufactured at this time was 0.4061 g / cm 3 am.

[0172]

[0173] Figure 2 shows scanning electron microscope (FE-SEM) analysis images of catalysts manufactured according to Manufacturing Examples 1, 3, and 4.

[0174] Specifically, FIG. 2(a) shows a scanning electron microscope (FE-SEM) analysis image of a catalyst manufactured according to Manufacturing Example 1, FIG. 2(b) shows a scanning electron microscope (FE-SEM) analysis image of a catalyst manufactured according to Manufacturing Example 3, and FIG. 2(c) shows a scanning electron microscope (FE-SEM) analysis image of a catalyst manufactured according to Manufacturing Example 4.

[0175] Referring to Fig. 2(a), it can be confirmed that the catalyst manufactured according to Manufacturing Example 1 is a mixture of secondary particles in which particles on the specimen are agglomerated and secondary particles in which particles of irregular shape are agglomerated.

[0176] Referring to Fig. 2(b), it can be confirmed that the catalyst manufactured according to Manufacturing Example 3 has a hexagonal secondary particle shape formed by generally stacking hexagonal specimen-shaped particles face to face based on a wide surface.

[0177] Referring to Fig. 2(c), it can be confirmed that the catalyst manufactured according to Manufacturing Example 4 is a mixture of hexagonal secondary particles in which similar sample-shaped particles as in Manufacturing Example 3 are stacked, irregularly shaped small-sized particles located on the surface thereof, small-sized secondary particles formed by agglomeration of multiple small particles, and single-sized particles. Meanwhile, the catalyst manufactured according to Manufacturing Example 4 contains a large amount of irregular particles and single-sized particles in the form of small-sized particles, which may cause problems such as operational problems due to clogging of the separator caused by the small particle size during the catalyst separation process in the polyol manufacturing process, and a decrease in the amount of catalyst recovered. Therefore, it was determined that it is not suitable for application to a polyol manufacturing process in which the catalyst is repeatedly used.

[0178]

[0179] (Example 1: Experiment on polyol production using DMC-AA-PAA)

[0180] According to the above Manufacturing Example 2, 0.11 g of the DMC-AA-PAA catalyst prepared in this manner was placed in a high-pressure reactor together with 90 mL of toluene, and the reactor was sealed. Thereafter, the interior of the reactor was purged with CO2 gas, and the CO2 pressure was controlled while heating the reactor to 115°C. While maintaining the final reactor internal temperature at 115°C and the internal pressure at 20 barg, propylene oxide (PO) and polypropylene glycol (PPG-1000, Kumho Petrochemical) were introduced at a rate of 1 g / min while stirring the materials inside the reactor, and the reaction was performed for 2 hours while stirring under the above temperature and pressure conditions. After completion of the reaction, the catalyst was separated from the materials inside the reactor using a filter to obtain the product. Propylene carbonate (PC) formed by the side reaction was separated and subjected to liquid-liquid separation and purification to obtain the final polyol. 1 L of distilled water and 50 g of chloroform were added to the product from which the catalyst had been removed, stirred, and separated into an upper layer and a lower layer. Then, the chloroform contained in the separated lower layer was evaporated under vacuum to obtain the final polyether carbonate polyol.

[0181]

[0182] (Example 2: Experiment on polyol production using DMC-MA-PAA)

[0183] A polyol was prepared in the same manner as in Example 1, except that DMC-MA-PAA prepared according to Manufacturing Example 3 was used instead of the DMC-AA-PAA catalyst prepared according to Manufacturing Example 2.

[0184]

[0185] (Comparative Example 1: Polyol manufacturing experiment using DMC-MA-P123)

[0186] A polyol was prepared in the same manner as in Example 1, except that DMC-AA-P123 prepared according to Manufacturing Example 1 was used instead of the DMC-AA-PAA catalyst prepared according to Manufacturing Example 2.

[0187]

[0188] The weight molecular weight, PDI, polyol selectivity, polyol carbonate content, and functional group number of the polyols manufactured according to Examples 1 to 2 and Comparative Example 1 are summarized in Table 1 below.

[0189]

[0190] The manufactured polyether carbonate polyol was subjected to H-NMR spectroscopy analysis (400 MHz Spectrometer, Varian) to measure the molecular weight, carbonate selectivity, and content. Specifically, 1 In H-NMR spectroscopy, a carbonate peak appears around 4.5 ppm, an ether peak appears around 3.5 ppm, and an initiator branch peak appears around 0.8 ppm. Using these, the molecular weight, carbonate selectivity, and carbonate content were calculated using the following equations 1 to 3, respectively.

[0191] Molecular weight = (initiator molecular weight) + (carbonate peak area * 10.5 * 142) + (ether peak area * 10.5 * 98) (1)

[0192] Carbonate selectivity = [(carbonate peak area) / (carbonate peak area)+(ether peak area)] * 100 (2)

[0193] Carbonate content = {(calculated molecular weight - initiator molecular weight) / (calculated molecular weight)} * carbonate selectivity * (44 / 142) (3)

[0194] (10.5 represents the ratio of hydrogen atoms in the molecule, and 142, 98, 44, and 142 represent the molecular weights of the molecular repeating units.)

[0195] Meanwhile, the above hydroxyl value was measured by the ASTM E 1899-97 method, and the OHv unit is mgBu4OH / g, and the above functional group number corresponds to the hydroxyl value contained per molecule of the polyol of the final product, polyether carbonate.

[0196]

[0197] Catalyst Mn (g / mol) PDI Selectivity Carbonate content in polyol (%) Functional group Polyol (%) PC (%) Comparative Example 1 DMC-AA-P1233, 100 1.55 67.6 32.4 9.6 2.7 ~ 3.0 Example 1 DMC-AA-PAA3, 200 1.60 68.4 31.6 10.9 2.8 Example 2 DMC-MA-PAA3, 700 1.37 89.0 11.0 14.3 2.7

[0198] Referring to Table 1 above, in the case of Examples 1 and 2, the selectivity of the manufactured polyol was found to be 68% or more, and the molecular weight was found to be 3200 g / mol and 3700 g / mol, respectively, which was greater than that of Comparative Example 1.

[0199] Additionally, for Examples 1 and 2, the carbonate content in the manufactured polyol was 10.9% and 14.3%, respectively, which was higher than that of Comparative Example 1.

[0200] Meanwhile, in the case of Examples 1 and 2, the functional groups were measured to be 2.8 and 2.7, respectively, and in the case of Comparative Example 1, it was confirmed to be approximately 2.7 to 3.0.

[0201]

[0202] The present invention is not limited to the above-described embodiments, but can be manufactured in a variety of different forms. Those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. Containing metal salts, metal cyanides, complexing agents and co-complexing agents, The above complexing agent is a homopolymer having a weight average molecular weight of 5500 g / mol or less. Double metal cyanide catalyst.

2. In paragraph 1, The above-mentioned complexing agent comprises at least one selected from polyacrylic acid polymer, polyethylene glycol, polypropylene glycol, copolymers or mixtures thereof. Double metal cyanide catalyst.

3. In paragraph 1, The above complexing agent comprises at least one selected from acrylic or methacrylic compounds. Double metal cyanide catalyst.

4. In paragraph 3, The above acrylic or methacrylic compound comprises at least one selected from the following chemical formulas 1-2 to 1-2: Double metal cyanide catalyst. [Chemical Formula 1-1] [Chemical Formula 1-2] 5. In paragraph 1, The above double metal cyanide catalyst is a compound represented by the following chemical formula 1: Double metal cyanide catalyst. [Chemical Formula 1] M a [M' (CN) 6 )] b ·L c ·L' d (In Chemical Formula 1, M is one selected from zinc (II), iron (II), iron (III), nickel (II), manganese (II), cobalt (II), tin (II), lead (II), molybdenum (IV), molybdenum (VI), aluminum (III), vanadium (V), vanadium (IV), strontium (II), tungsten (IV), tungsten (VI), copper (II), and chromium (III), M' is one selected from iron (II), iron (III), cobalt (II), cobalt (III), chromium (II), chromium (III), manganese (II), manganese (III), iridium (III), nickel (II), rhodium (III), ruthenium (II), vanadium (V), and vanadium (IV). L contains acrylic or methacrylic compounds as complexing agents, L' contains a hydrophilic homopolymer as a complexing agent, a, b, c and d are positive numbers.) 6. In paragraph 1, The apparent density of the above double metal cyanide catalyst is 0.30 g / cm 3 0.60g / cm2 3 It is, Double metal cyanide catalyst.

7. In paragraph 1, The above double metal cyanide catalyst is, It is a secondary particle in which layered nanosheets are laminated. Double metal cyanide catalyst.

8. In paragraph 7, The average major axis length of the wide surface of the above layered nanosheet is 1.0 ㎛ to 15.0 ㎛. Double metal cyanide catalyst.

9. In paragraph 7, The average short axis length of the wide surface of the above layered nanosheet is in the range of 1 / 7 to 6 / 7 of the average long axis length. Double metal cyanide catalyst.

10. In paragraph 7, The average thickness of the above nanosheets is 25 nm to 85 nm. Double metal cyanide catalyst.

11. A step of preparing a first solution containing a metal salt, a complexing agent, and water; A step of preparing a second solution containing a metal cyanide salt and water; A step of preparing a third solution containing a complexing agent and a co-complexing agent; A step of preparing a fourth solution by mixing the first solution and the second solution; A first reaction step of adding the third solution to the fourth solution and reacting; A second reaction step of separating the precipitate formed in the first reaction step and then mixing the separated precipitate with a solution containing water and a complexing agent to react; After the completion of the second reaction step, a third reaction step is performed by adding a fifth solution containing a complexing agent and a co-complexing agent; and A step of separating the precipitate formed in the third reaction step; The above-mentioned complexing agent is a homopolymer having a weight average molecular weight of 5500 g / mol or less. Method for producing a double metal cyanide catalyst.

12. In paragraph 11, In the step of preparing a first solution containing the metal salt, a complexing agent and water, Mixing the above metal salt, complexing agent and water and heating to a temperature of 50°C to 90°C, Method for producing a double metal cyanide catalyst.

13. In paragraph 11, In the step of preparing a second solution containing the metal cyanide and water, Mix the above metal cyanide and water and heat to a temperature of 50℃ to 70℃. Method for producing a double metal cyanide catalyst.

14. In paragraph 11, In the step of preparing a first solution containing the metal salt, a complexing agent and water, Mixing 0.04 mol to 1.0 mol of the complexing agent per 1.0 mol of the water, Method for producing a double metal cyanide catalyst.

15. In paragraph 11, In the step of preparing a third solution containing the above complexing agent and co-complexing agent, The molar ratio of the complexing agent to the above complexing agent (complexing agent: complexing agent) is 600:1 to 1200:

1. Method for producing a double metal cyanide catalyst.

16. In paragraph 11, After the completion of the above second reaction step, in the third reaction step, a fifth solution containing a complexing agent and a co-complexing agent is added to react. The molar ratio of the complexing agent to the complexing agent in the fifth solution is 150:1 to 1250:

1. Method for producing a double metal cyanide catalyst.

17. In paragraph 11, In the step of preparing a fourth solution by mixing the first and second solutions, The molar ratio of metal cyanide to metal salt in the fourth solution manufactured above (metal cyanide:metal salt) is 2:1 to 30:

1. Method for producing a double metal cyanide catalyst.

18. In paragraph 11, The above second reaction step and third reaction step are performed twice or more. Method for producing a double metal cyanide catalyst.

19. In paragraph 11, In the step of separating the precipitate formed in the third reaction step, a step of washing and drying the separated precipitate is further included. Method for producing a double metal cyanide catalyst.

20. In paragraph 19, In the step of washing and drying the separated sediment, the sediment is washed using water. Method for producing a double metal cyanide catalyst.

21. A step of introducing a double metal cyanide catalyst and a solvent according to any one of claims 1 to 10 into a reactor; CO 2 After purging the inside of the reaction chamber using gas, the reactor is heated while CO 2 Step of regulating pressure with gas; A step of forming a product by introducing an initiator and an epoxy compound into the reactor; and A step of separating polyol within the above product; comprising: Method for producing polyol.

22. In paragraph 21, The above initiator is a compound represented by the following chemical formula 2: Method for producing polyol. [Chemical formula 2] (In chemical formula 2, R is H or an alkyl group having 1 carbon atom, and n is an integer within the range of 1 to 227.) 23. In paragraph 21, The above epoxy compound is a compound represented by the following chemical formula 3: Method for producing polyol. [Chemical Formula 3] (In chemical formula 3, R is H, -CH 3 , -CH 3 OH, methyl halide (-CH 3 F, -CH 3 Cl, -CH 3 Br) and an alkyl group having 1 to 8 carbon atoms.) 24. In paragraph 21, The weight average molecular weight of the above polyol is 3000 g / mol to 5000 g / mol, Method for producing polyol.

25. In paragraph 21, The polydispersity index (PDI) of the above polyol is 1.65 or less. Method for producing polyol.

26. In paragraph 21, The selectivity of the above polyol is 65% or more, Method for producing polyol.

27. In paragraph 21, The functional group number of the above polyol is 2.5 or more, Method for producing polyol.

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