Method for preparing high-functional polyethercarbonate polyol, polyethercarbonate polyol and rigid polyurethane foam prepared using the same

Abstract

The present invention relates to a method for producing a highly functional polyether carbonate polyol, a polyether carbonate polyol produced using the same, and a rigid polyurethane foam. By using an initiator containing a large amount of functional groups without reducing the activity of the catalyst during the polymerization reaction of carbon dioxide and an alkylene oxide compound under a bimetallic cyanide catalyst, a polyether carbonate polyol for rigid polyurethane foam containing a large amount of carbon dioxide and having a high carbonate content can be obtained in high yield.

Description

Technology Field

[0001] The present invention relates to a method for producing a high-functionality polyether carbonate polyol that can be used in the manufacture of rigid polyurethane foam, a polyether carbonate polyol produced using the same, and rigid polyurethane foam. Background Technology

[0003] Generally, when polyurethane foam is produced using a polyol with 1 to 2 alcohol groups, a soft foam can be obtained, whereas when polyurethane foam is produced using a polyol with 3 or more alcohol groups, a rigid foam can be obtained.

[0004] In the polymerization reaction of carbon dioxide and alkylene oxide compounds using conventional bimetallic cyanide catalysts, when a substance containing a large amount of functional groups such as glycerol or pentaerythritol is used as an initiator, there was a problem in that copolymerization between carbon dioxide and alkylene oxide compounds did not proceed as the activity of the catalyst was reduced or lost due to the chelation action of the bimetallic cyanide catalyst with the metal.

[0005] In addition, conventional methods using bimetallic cyanide catalysts produced polyols having two or fewer functional groups due to chelation with the metal in the catalyst, which were suitable only for soft foams. Therefore, for the production of hard foams, there was a disadvantage in that separate additives for hard foams and additional functional group measurements were required during the polyurethane manufacturing stage.

[0006] Accordingly, the inventors developed a method for producing a highly functional polyether carbonate polyol using a novel initiator that does not reduce the activity of the catalyst during the polymerization reaction of carbon dioxide and alkylene oxide compounds under a bimetallic cyanide catalyst, and confirmed the characteristics of the polyether carbonate polyol produced by this method to complete the present invention. Prior art literature

[0008] Republic of Korea Registered Patent No. 10-1980744 (Published May 21, 2019) The problem to be solved

[0009] The objective of the present invention is to provide a novel initiator that does not reduce the activity of the catalyst during the polymerization reaction of carbon dioxide and alkylene oxide compounds under a bimetallic cyanide catalyst, a method for producing a polyether carbonate polyol using the same, a polyether carbonate polyol produced using the same, and a rigid polyurethane foam.

[0010] Another object of the present invention is a method for producing a highly functional polyethercarbonate polyol having a high carbonate content containing a large amount of carbon dioxide by using an initiator containing a large amount of functional groups, a polyethercarbonate polyol produced using the same, and a rigid polyurethane foam.

[0011] Another objective of the present invention is to provide a method for manufacturing a polyether carbonate polyol that can be used for rigid polyurethane foam, a polyether carbonate polyol manufactured using the same, and a rigid polyurethane foam.

[0012] The problems that the present invention aims to solve are not limited to the problem(s) mentioned above, and other unmentioned problems will be clearly understood by those skilled in the art from the description below. means of solving the problem

[0014] According to one aspect of the present invention, the present invention provides a method for producing a polyether carbonate polyol, comprising copolymerizing an initiator represented by Formula 1, carbon dioxide, and an alkyl epoxy compound represented by Formula 2 under an epoxy ring-opening catalyst to synthesize a polyether carbonate polyol represented by Formula 3.

[0015] [Chemical Formula 1]

[0016]

[0017] [Chemical Formula 2]

[0018]

[0019] [Chemical Formula 3]

[0020]

[0021] In the above chemical formula 1, R 1, R 2, R3 and R4 is each independently substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and said substituent is an alkyl group having 1 to 10 carbon atoms, and

[0022] In the above chemical formula 2, R 5, R 6, R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl groups, alkyl ethers, alkylaryls, and aryls, and

[0023] In the above chemical formula 3, R 1, R 2, R3 and R4 is each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, said substituent is an alkyl group having 1 to 10 carbon atoms, and [A], [B], [C], and [D] are each independently and x is an integer from 1 to 50, and R 5, R 6, R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkyl ethers, alkylaryls, and aryls, and k, l, m, and n are each independently integers from 1 to 50.

[0024] The above epoxy ring-opening catalyst may be selected from the group consisting of bimetallic cyanide, potassium hydroxide, or zinc glutarate.

[0025] The above epoxy ring-opening catalyst may be a bimetallic cyanide catalyst comprising a metal salt, a metal cyanide, and a complexing agent.

[0026] The above-mentioned bimetallic cyanide catalyst may be 50 ppm to 2000 ppm with respect to the total composition.

[0027] The above initiator may be pentaerythritol propoxylate or pentaerythritol ethoxylate.

[0028] The above alkyl epoxy compound may be in a molar ratio of 1 to 100 times with respect to the initiator.

[0029] The pressure of the carbon dioxide may be 5 to 30 bar.

[0030] The above alkyl epoxy compound may further include any one selected from the following chemical formula 4.

[0031] [Chemical Formula 4]

[0032]

[0033] In the above formula, R9 is any one selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, alkyl ether, alkylaryl group, and aryl group, Z is a halogen, and Y is any one selected from the group consisting of oxygen, CH2, and an alkyl group.

[0034] In the above manufacturing method, the reaction temperature may be 90 to 150 ℃.

[0035] According to another aspect of the present invention, the present invention provides a polyether carbonate polyol represented by the following chemical formula 3.

[0036] [Chemical Formula 3]

[0037]

[0038] In the above formula,

[0039] R 1, R 2, R3 and R4 is each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, said substituent is an alkyl group having 1 to 10 carbon atoms, and [A], [B], [C], and [D] are each independently and x is an integer from 1 to 50, and R 5, R 6, R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkyl ethers, alkylaryls, and aryls, and k, l, m, and n are each independently integers from 1 to 50.

[0040] The above polyether carbonate polyol may have three or more alcohol groups.

[0041] The above polyether carbonate polyol may have a number average molecular weight (Mn) of 500 to 5,000 g / mol.

[0042] The above polyether carbonate polyol may have a carbonate content of 3 to 40 mol%.

[0043] According to another aspect of the present invention, the present invention provides a rigid polyurethane foam manufactured by including the aforementioned polyethercarbonate polyol. Effects of the invention

[0045] According to the present invention, by using a novel initiator that does not reduce the activity of the catalyst during the polymerization reaction of carbon dioxide and alkylene oxide compounds under a bimetallic cyanide catalyst, the yield of polyether carbonate polyol is excellent.

[0046] According to the present invention, the manufacturing method is performed as a single-step reaction, which simplifies the process and has the effect of increasing economic efficiency.

[0047] According to the present invention, by using an initiator containing a large amount of functional groups, there is an effect of providing a method for producing a polyether carbonate polyol that can be used for a rigid urethane foam having a high carbonate content containing a large amount of carbon dioxide, a polyether carbonate polyol produced using the same, and a rigid polyurethane foam.

[0048] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description of the invention or the claims. Brief explanation of the drawing

[0050] Figure 1 shows a process flow diagram of a method for manufacturing a polyether carbonate polyol according to one embodiment of the present invention. Figure 2 shows a scanning electron microscope image of a polyurethane foam manufactured using a polyether carbonate polyol according to one embodiment of the present invention. Specific details for implementing the invention

[0051] Before describing the present invention in detail, it should be understood that the terms and words used in this specification should not be interpreted as being limited to their ordinary or dictionary meanings, and that the inventor of the present invention may appropriately define and use the concepts of various terms to best describe their invention, and furthermore, that these terms and words should be interpreted in a meaning and concept consistent with the technical spirit of the present invention.

[0052] In other words, it should be understood that the terms used in this specification are used merely to describe preferred embodiments of the present invention and are not intended to specifically limit the content of the present invention, and that these terms are defined in consideration of the various possibilities of the present invention.

[0053] In addition, it should be noted that in this specification, singular expressions may include plural expressions unless the context clearly indicates a different meaning, and that even if they are expressed in a similarly plural form, they may include a singular meaning.

[0054] Throughout this specification, where it is stated that a component "includes" another component, unless specifically stated otherwise, this may mean that it does not exclude any other component but may include any other component.

[0055] In addition, in describing the present invention below, detailed descriptions of components, such as prior art and known technology, that are deemed to unnecessarily obscure the essence of the invention may be omitted.

[0056] The present invention will be described in more detail below.

[0058] Method for manufacturing polyether carbonate polyol

[0059] Figure 1 is a process flow diagram of the method for manufacturing a polyether carbonate polyol according to the present invention.

[0060] Referring to FIG. 1, the method includes synthesizing a polyether carbonate polyol by copolymerizing an initiator, carbon dioxide, and an alkyl epoxy compound under an epoxy ring-opening catalyst.

[0061] The above epoxy ring-opening catalyst may be selected from the group consisting of bimetallic cyanide, potassium hydroxide (KOH), or zinc glutarate (Salen), and among these, it is preferable to use a bimetallic cyanide catalyst.

[0062] The above epoxy ring-opening catalyst may be a bimetallic cyanide catalyst comprising a metal salt, a metal cyanide, and a complexing agent.

[0063] The above complexing agent uses an organic alcohol compound (n= 2, 3, …, n-1) in which a hydroxyalkyl group is substituted on the nth carbon of an oxacycloalkane ring, wherein the alkyl group of the hydroxyalkyl group is C1 to C20, and the alkyl group may be a substituted or unsubstituted alkyl group.

[0064] At this time, as the complexing agent (CA), an organic alcohol compound (n=2) in which a hydroxyalkyl group is substituted on the nth carbon of the oxacyclopropane ring can be used.

[0065] In addition, as the complexing agent (CA), an organic alcohol compound (n=2 or 3) in which a hydroxyalkyl group is substituted on the nth carbon of an oxacyclobutane ring can be used.

[0066] In addition, as the complexing agent (CA), an organic alcohol compound (n=2, 3, or 4) in which a hydroxyalkyl group is substituted on the nth carbon of the oxacyclopentane ring can be used.

[0067] In addition, as the complexing agent (CA), an organic alcohol compound (n=2, 3, 4 or 5) in which a hydroxyalkyl group is substituted on the nth carbon of an oxacyclohexane ring can be used.

[0068] At this time, the alkyl group of the hydroxyalkyl group may preferably be C1 to C18, and more preferably C1 to C15.

[0069] In addition, the complexing agent (CA) may be any one selected from 3-hydroxytetrahydrofuran, tetrahydrofuran-2-methanol, tetrahydrofuran-2-ethanol, tetrahydrofuran-3-methanol, tetrahydrofuran-3-ethanol, tetrahydropyran-2-methanol, tetrahydropyran-2-ethanol, tetrahydropyran-3-methanol, tetrahydropyran-3-methanol, tetrahydropyran-4-methanol, tetrahydropyran-4-ethanol, and oxiran-2-yl-methanol.

[0070] Conventional bimetallic cyanide complexing agents commonly use tert-butyl alcohol (t-BuOH) or dioxane.

[0071] However, when using conventional bimetallic cyanide catalysts, polymer impurities are generated, which causes problems when synthesizing polyether carbonate polyols (polyalcohol polyols) for rigid polyurethane foams, and it has been reported that the bimetallic cyanide catalysts do not control the explosive reaction temperature (hot spot) during the reaction, leading to a problem of rising reaction temperature.

[0072] To solve this, the present invention intended to produce a polyether carbonate polyol for rigid polyurethane foam using a bimetallic cyanide catalyst.

[0073] At this time, when using a bimetallic cyanide catalyst prepared using the complexing agent according to the present invention instead of tert-butyl alcohol (t-BuOH) or dioxane used as conventional complexing agents, there is an advantage in being able to control the explosive reaction temperature during the reaction.

[0074] For example, when using a highly reactive alkyl epoxy compound, an explosive reaction temperature (hot spot) occurs due to the reactivity. However, when using a bimetallic cyanide catalyst prepared using the complexing agent according to the present invention, the reactivity of the alkyl epoxy compound can be reduced so that an explosive reaction temperature does not occur.

[0075] The concentration of the above-mentioned bimetallic cyanide catalyst may be 50 ppm to 2000 ppm (mg / kg) with respect to the total composition (catalyst, initiator, and alkyl epoxy compound), preferably 60 ppm to 1900 ppm, and more preferably 70 ppm to 1800 ppm. In this case, if the concentration of the above-mentioned bimetallic cyanide catalyst is within the above range, the activity of the polymerization reaction may be increased.

[0076] The present invention provides a novel initiator that can be used in the polymerization reaction of carbon dioxide and alkylene oxide compounds using a bimetallic cyanide catalyst.

[0077] In the polymerization reaction of carbon dioxide and alkylene oxide compounds using conventional bimetallic cyanide catalysts, when a substance containing a large amount of functional groups such as glycerol or pentaerythritol is used as an initiator, there was a problem in that copolymerization between carbon dioxide and alkylene oxide compounds did not proceed as the activity of the catalyst was reduced or lost due to the chelation action of the bimetallic cyanide catalyst with the metal.

[0078] The present invention provides a method for producing a polyether carbonate polyol using a novel initiator that contains a large amount of functional groups and does not reduce the activity of the bimetallic cyanide catalyst, as an initiator used in the polymerization reaction of carbon dioxide and alkylene oxide compounds under a bimetallic cyanide catalyst to solve the above-mentioned problems.

[0079] The above initiator may be represented by the following chemical formula 1.

[0080] [Chemical Formula 1]

[0081]

[0082] In the above chemical formula 1, R 1, R 2, R3 and R4 is each independently substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and the substituent is an alkyl group having 1 to 10 carbon atoms.

[0083] The above initiator may be pentaerythritol alkoxylate, and preferably may be pentaerythritol propoxylate or pentaerythritol ethoxylate.

[0084] The above initiator may be present in a molar ratio of 0.01 to 1 with respect to the alkyl epoxy compound, and preferably in a molar ratio of 0.01 to 0.1. If the ratio falls outside this range, it may be difficult to insert carbon dioxide, which may result in a problem of lower carbonate content or lower yield.

[0085] The present invention provides a method for producing a highly functional polyether carbonate polyol having a high carbonate content containing a large amount of carbon dioxide through a polymerization reaction of carbon dioxide and an alkylene oxide compound with an initiator containing a large amount of functional groups under a bimetallic cyanide catalyst.

[0086] The pressure of the carbon dioxide may be 5 to 30 bar, and preferably 5 to 20 bar. Below this range, there may be a problem where it is difficult to form carbonates within the polyol structure due to insufficient supply of carbon dioxide, and above this range, there may be a problem where high costs are incurred in manufacturing the reactor and excessive energy waste occurs.

[0087] The above alkyl epoxy compound may be represented by Chemical Formula 2.

[0088] [Chemical Formula 2]

[0089]

[0090] In the above chemical formula 2, R 5, R 6, R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkyl ether groups, vinyl ether groups, alkyl ester groups, alkyl aryl groups, aryl groups, oxygen-containing cycloalkyl groups, methylene-containing cycloalkyl groups, halogen-containing cycloalkyl groups, and halogen alkyl groups.

[0091] In the above alkyl epoxy compound, two substituents selected from R5 to R8 form a ring to form a cyclic epoxy compound, and the formed cyclic epoxy compound further comprises substituents, and the substituents may be substituted or unsubstituted alkyl groups having 4 to 20 carbon atoms or alkyl ethers.

[0092] Here, the alkyl epoxy compound may further include any one selected from the following chemical formula 4, but is not limited thereto.

[0093] [Chemical Formula 4]

[0094]

[0095] The above R9 is any one selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl groups, alkyl ethers, alkylaryls, and aryls, Z is a halogen, and Y is any one selected from the group consisting of oxygen, CH2, and alkyl groups.

[0096] The above alkyl epoxy compound may be in a molar ratio of 1 to 100 times with respect to the initiator, and preferably in a molar ratio of 20 to 80 times. If the ratio is outside the above range, there may be a problem in that the reaction does not proceed well.

[0097] Under the epoxy ring-opening catalyst of the present invention, the synthesis of a polyether carbonate polyol represented by Formula 3 by copolymerizing an initiator represented by Formula 1, carbon dioxide, and an alkyl epoxy compound represented by Formula 2 is characterized by being carried out as a single-step reaction. In the case of the prior art, Patent Application No. 10-2023-0037145, a carboxylic acid compound is used as an initiator, and since the viscosity of the initiator itself is high, the reaction is carried out in two steps; however, in the case of the present invention, pentaerythritol alkoxylate is used as an initiator and carried out in a single step, thereby simplifying the process and increasing economic efficiency.

[0098] The above reaction may be carried out at a temperature of 90 to 150 ℃, and preferably at a temperature of 100 to 140 ℃. If the reaction temperature is below 90 ℃, the reaction time may become too long, and if the reaction temperature exceeds 150 ℃, the pressure of the reactor may become excessively high and the reactants may decompose.

[0099] The above reaction may be carried out in a solvent. Specifically, an initiator, carbon dioxide, and an alkyl epoxy compound may be introduced into a solvent and reacted. The solvent may be a solvent commonly used in the technical field of the present invention and may be an organic solvent such as toluene, but is not limited thereto.

[0100] In the present invention, the polyether carbonate polyol synthesized by copolymerizing an initiator, carbon dioxide, and an alkyl epoxy compound under an epoxy ring-opening catalyst may be represented by the following chemical formula 3.

[0101] [Chemical Formula 3]

[0102]

[0103] In the above chemical formula 3, R 1, R 2, R3 and R4 is each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, said substituent is an alkyl group having 1 to 10 carbon atoms, and [A], [B], [C], and [D] are each independently and x is an integer from 1 to 50, and R 5, R 6, R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkyl ethers, alkylaryls, and aryls, and k, l, m, and n are each independently integers from 1 to 50.

[0105] Polyethercarbonate polyol

[0106] The present invention provides a polyether carbonate polyol prepared by the method for preparing a polyether carbonate polyol described above and represented by the following chemical formula 3.

[0107] [Chemical Formula 3]

[0108]

[0109] In the above formula,

[0110] R 1, R 2, R3 and R4 is each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, said substituent is an alkyl group having 1 to 10 carbon atoms, and [A], [B], [C], and [D] are each independently and x is an integer from 1 to 50, and R 5, R 6,R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkyl ethers, alkylaryls, and aryls, and k, l, m, and n are each independently integers from 1 to 50.

[0111] Specifically, the polyether carbonate polyol prepared in one embodiment of the present invention can be represented by the following chemical formula 3-1.

[0112] [Chemical Formula 3-1]

[0113]

[0114] In the above formula, k, l, m, and n are each independently integers from 1 to 50, and x is each independently integer from 1 to 50.

[0115] The above polyether carbonate polyol may have three or more alcohol groups, and thus the above polyether carbonate polyol may be used for rigid polyurethane foam. Since the polyether carbonate polyol according to the present invention has a hydroxyl value of 3 to 10 and can be used for rigid polyurethane foam, it can be widely used for thermal insulation materials, lightweight structural materials, cushioning materials, etc. Generally, when using a bimetallic cyanide catalyst, the efficiency of the catalyst may decrease due to chelation when the hydroxyl value (OH value) is 3 or higher; however, the present invention has the advantage of being able to efficiently synthesize a polyether carbonate polyol with a hydroxyl value (OH value) of 3 to 10 by using a novel initiator that does not reduce the activity of the bimetallic cyanide catalyst. In addition, if the hydroxyl value (OH value) of the polyether carbonate polyol is within the above range, it may be possible to synthesize a rigid foam polyurethane by reacting with an isocyanate (NCO) compound.

[0116] The above polyether carbonate polyol may have a number average molecular weight (Mn) of 500 to 5,000 g / mol. The number average molecular weight of the above polyether carbonate polyol refers to the value obtained by dividing the total mass by the number of chains.

[0117] The above polyether carbonate polyol may have a carbonate content of 3 to 40 mol%. Therefore, since the carbon dioxide (CO2) content in the polyether carbonate polyol is high, it has an eco-friendly effect by removing carbon dioxide that can cause environmental pollution, and it can be seen as having great environmental value in that it recycles carbon dioxide and converts it into a high-value compound.

[0119] Rigid polyurethane foam

[0120] The present invention provides a rigid polyurethane foam manufactured by including the aforementioned polyethercarbonate polyol.

[0121] As described above, the polyether carbonate polyol according to the present invention has three or more alcohol groups and a hydroxyl value of 3 to 10, making it suitable for manufacturing rigid polyurethane foam. Accordingly, the polyurethane foam manufactured including the polyether carbonate polyol according to the present invention is rigid and can be widely used as thermal insulation, lightweight structural material, cushioning material, etc.

[0123] Examples

[0124] Hereinafter, the present invention will be described in detail with reference to examples in order to specifically explain the invention. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention should not be interpreted as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the invention to those with average knowledge in the art.

[0126] <Preparation of Polyether Carbonate Polyols>

[0127] Example 1

[0128] 150 g of solvent (toluene), 2.5 mol (145.2 g) of propylene oxide (PO), 17.75 g (0.04 mol) of pentaerythritol propoxylate as an initiator, and 162.95 mg (1000 ppm) of a bimetallic cyanide catalyst were placed in a 450 ml high-pressure reactor and sealed. The reactor was purged while maintaining the internal pressure at 1.0–1.5 barg of carbon dioxide gas. Subsequently, 20 barg of carbon dioxide was added at room temperature, the temperature was raised to 115 ℃, and the polymerization reaction was carried out at 600 rpm for 2 hours. During the reaction, carbon dioxide was continuously injected to maintain the internal pressure of the reactor so that it did not drop below 20 barg. After 2 hours, the injection of carbon dioxide gas and heating were stopped, the remaining carbon dioxide gas inside was removed, and the reactor was unsealed to obtain the reaction product. Polyether carbonate polyol was obtained by removing unreacted monomers and solvent from the reaction product using a rotary evaporator.

[0129] The above-mentioned bimetallic cyanide catalyst is prepared using tetrahydrofurfuryl alcohol as an organic complexing agent, and specifically as follows.

[0130] A primary solution was prepared by dissolving 3.0 g of potassium hexacyanocobaltate (K3Co(CN)6) in 49 mL of distilled water in a 500 mL flask. A secondary solution was prepared by dissolving 28.3 g of zinc chloride (ZnCl2) in a mixed solution of 44 mL of tetrahydrofurofuryl alcohol (THFA) (50 equivalents relative to potassium hexacyanocobaltate (K3Co(CN)6)) and 81 mL of distilled water (500 equivalents relative to potassium hexacyanocobaltate (K3Co(CN)6)). The primary solution was added dropwise to the secondary solution over 30 minutes while stirring at 50 °C, and after reacting for 1.5 hours, a precipitate (A) was obtained using a centrifuge.

[0131] Subsequently, the following washing process was performed. The washing process was repeated by adding the precipitate (A) to a mixed solution of tetrahydrofurofuryl alcohol (THFA) and distilled water, stirring at room temperature for 2 to 3 minutes, and then centrifuging to obtain precipitate (B). At this time, the number of washes and the amounts of tetrahydrofurofuryl alcohol (THFA) and distilled water were as follows: 1st wash: THFA (44 mL), distilled water (70 mL) / 2nd wash: THFA (44 mL), distilled water (35 mL) / 3rd wash: THFA (44 mL), distilled water (10 mL) / 4th wash: THFA (60 mL). After the washing process, the solid obtained after centrifugation was dried using an oven at 50 ℃ and a vacuum oven until the weight did not change to prepare a bimetallic cyanide catalyst.

[0133] Example 2

[0134] Polyether carbonate polyols were prepared in the same manner as in Example 1, except that 21.3 g (0.05 mol) of pentaerythritol propoxylate and 166.5 mg (1000 ppm) of a bimetallic cyanide catalyst were used as initiators.

[0136] Example 3

[0137] Polyether carbonate polyols were prepared in the same manner as in Example 2 above, except that 26.63 g (0.06 mol) of pentaerythritol propoxylate and 171.83 mg (1000 ppm) of a bimetallic cyanide catalyst were used as initiators.

[0139] Example 4

[0140] Polyether carbonate polyols were prepared in the same manner as in Example 2 above, except that 35.5 g (0.08 mol) of pentaerythritol propoxylate and 180.7 mg (1000 ppm) of a bimetallic cyanide catalyst were used as initiators.

[0142] Example 5

[0143] Polyether carbonate polyols were prepared in the same manner as in Example 2 above, except that 33.21 g (0.04 mol) of pentaerythritol ethoxylate and 178.41 mg (1000 ppm) of a bimetallic cyanide catalyst were used as initiators.

[0145] Example 6

[0146] Polyether carbonate polyols were prepared in the same manner as in Example 2 above, except that 39.85 g (0.05 mol) of pentaerythritol ethoxylate and 185.05 mg (1000 ppm) of a bimetallic cyanide catalyst were used as initiators.

[0148] Example 7

[0149] Polyether carbonate polyols were prepared in the same manner as in Example 2 above, except that 49.81 g (0.06 mol) of pentaerythritol ethoxylate and 195.01 mg (1000 ppm) of a bimetallic cyanide catalyst were used as initiators.

[0151] Example 8

[0152] Polyether carbonate polyols were prepared in the same manner as in Example 2 above, except that 66.42 g (0.08 mol) of pentaerythritol ethoxylate and 211.62 mg (1000 ppm) of a bimetallic cyanide catalyst were used as initiators.

[0154] Comparative Example 1

[0155] Polyether carbonate polyol was prepared in the same manner as in Example 2 above, except that 21.3 g (0.23 mol) of glycerol was used as an initiator.

[0157] Comparative Example 2

[0158] Polyether carbonate polyol was prepared in the same manner as in Example 2 above, except that 21.3 g (0.16 mol) of pentaerythritol was used as an initiator.

[0160] Manufacture of Rigid Polyurethane Foam

[0161] Example 9

[0162] The polyol prepared in Example 2, diethylene glycol, Polycat 8, water, and Niax L-5420 were weighed in the amounts listed in Table 1 and mixed for 3 minutes until uniformly mixed. Subsequently, an isocyanate compound (M-200) was added and mixed for 30 seconds, after which the mixture was poured into a mold and foamed. The polyurethane prepared through the above process was cured at room temperature for 24 hours. Scanning electron microscope results of the cured polyurethane foam are shown in Figure 2. Referring to Figure 2, it was confirmed that the polyurethane foam prepared including the polyethercarbonate polyol of Example 2 was successfully prepared and cured.

[0163]

[0165] Experimental Example 1

[0166] For the polyether carbonate polyols prepared in Examples 1-8 and Comparative Examples 1-2, the yield, number average molecular weight (Mn), polydispersity index (PDI), and carbonate [-O-(C=O)-O-] content (since cyclic propylene carbonate, a byproduct containing carbonate, is excluded from the carbonate content calculation formula, the carbonate content and carbon dioxide content can be considered equal) were measured, and the results are shown in Table 2.

[0167]

[0168] Referring to Table 2, Comparative Example 1-2 did not properly synthesize polyether carbonate polyol, whereas Example 1-9 showed a high yield of polyether carbonate polyol and excellent number average molecular weight and polydispersity index, confirming that the polyether carbonate polyol was well synthesized. In addition, Example 1-9 was confirmed to be suitable for manufacturing rigid polyurethane foam because it has a high carbonate content.

[0170] Although specific embodiments regarding a method for manufacturing a high-functionality polyether carbonate polyol according to one embodiment of the present invention, a polyether carbonate polyol manufactured using the same, and a rigid polyurethane foam have been described so far, it is obvious that various modifications are possible within the scope of the present invention.

[0171] Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the claims set forth below as well as equivalents thereof.

[0172] That is, the aforementioned embodiments should be understood as exemplary in all respects and not limiting, and the scope of the invention is defined by the claims set forth below rather than by the detailed description, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the invention.

Claims

Claim 1 A method for producing a polyether carbonate polyol, comprising copolymerizing an initiator represented by Chemical Formula 1, carbon dioxide, and an alkyl epoxy compound represented by Chemical Formula 2 under an epoxy ring-opening catalyst to synthesize a polyether carbonate polyol represented by Chemical Formula 3, wherein the epoxy ring-opening catalyst is a bimetallic cyanide catalyst comprising zinc chloride (ZnCl2) as a metal salt, potassium hexacyanocobaltate (K3Co(CN)6) as a metal cyanide salt, and a complexing agent, and wherein the complexing agent is 3-hydroxytetrahydrofuran, tetrahydrofuran-2-methanol, tetrahydrofuran-2-ethanol, tetrahydrofuran-3-methanol, tetrahydrofuran-3-ethanol, tetrahydropyran-2-methanol, tetrahydropyran-2-ethanol, tetrahydropyran-3-methanol, A method for preparing a polyether carbonate polyol, characterized in that the polyol is selected from tetrahydropyran-3-ethanol, tetrahydropyran-4-methanol, tetrahydropyran-4-ethanol, and oxirane-2-yl-methanol, the synthesis is performed as a single-step reaction, and the carbonate content in the polyol prepared by the synthesis is 3 to 40 mol%. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formula 1, R 1, R 2, R3 and R4 is each independently substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, said substituent is an alkyl group having 1 to 10 carbon atoms, and in the above formula 2, R 5, R 6, R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl groups, alkyl ethers, alkylaryl groups, and aryl groups, and in the above formula 3, R 1, R 2, R3 and R4 is each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, said substituent is an alkyl group having 1 to 10 carbon atoms, and [A], [B], [C], and [D] are each independently and x is an integer from 1 to 50, and R 5, R 6, R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkyl ethers, alkylaryls, and aryls, and k, l, m, and n are each independently integers from 1 to 50. Claim 2 delete Claim 3 delete Claim 4 A method for producing a polyether carbonate polyol according to claim 1, characterized in that the bimetallic cyanide catalyst is present in an amount of 50 ppm to 2000 ppm relative to the total composition. Claim 5 A method for producing a polyether carbonate polyol, characterized in that, in claim 1, the initiator is pentaerythritol propoxylate or pentaerythritol ethoxylate. Claim 6 A method for producing a polyether carbonate polyol according to claim 1, characterized in that the alkyl epoxy compound is in a molar ratio of 1 to 100 times with respect to the initiator. Claim 7 A method for manufacturing a polyether carbonate polyol according to claim 1, characterized in that the pressure of the carbon dioxide is 5 to 30 bar. Claim 8 A method for preparing a polyether carbonate polyol according to claim 1, characterized in that the alkyl epoxy compound further comprises any one selected from the following Chemical Formula 4. [Chemical Formula 4] In the above formula, R9 is any one selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, alkyl ether, alkylaryl group, and aryl group, Z is a halogen, and Y is any one selected from the group consisting of oxygen, CH2, and an alkyl group. Claim 9 A method for manufacturing a polyether carbonate polyol according to claim 1, characterized in that the reaction temperature is 90 to 150 ℃. Claim 10 A polyether carbonate polyol represented by the following chemical formula 3, characterized in that it is manufactured by the method of claim 1, has a hydroxyl value (OH value) of 3 to 10, and has a carbonate content of 3 to 40 mol% in the polyether carbonate polyol. [Chemical Formula 3] In the above equation, R 1, R 2, R3 and R4 is each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, said substituent is an alkyl group having 1 to 10 carbon atoms, and [A], [B], [C] and [D] are each independently and x is an integer from 1 to 50, and R 5, R 6, R7 and R8 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkyl ethers, alkylaryls, and aryls, and k, l, m, and n are each independently integers from 1 to 50. Claim 11 A polyether carbonate polyol according to claim 10, characterized by having three or more alcohol groups. Claim 12 A polyether carbonate polyol according to claim 10, characterized by having a number average molecular weight (Mn) of 500 to 5,000 g / mol. Claim 13 delete Claim 14 Rigid polyurethane foam manufactured by including the polyether carbonate polyol of claim 10.

Images