Liquefied composition of propargyl carboxylate derivative used as electrolyte additive and preparation method therefor

Abstract

The present invention relates to: a method for preparing a liquefied propargyl carboxylate derivative used as a non-aqueous electrolyte additive for a lithium secondary battery represented by chemical formula 3 by reacting a starting material with a compound in the presence of a reactive organic solvent; and a liquid propargyl carboxylate composition produced thereby. The present invention has an effect of reducing manufacturing costs by performing liquefaction by simplifying a process in which manufacturing in a solid state was performed and then liquefaction was performed.

Description

Liquefaction composition of propargyl carboxylate derivative used as electrolyte additive and method for producing same

[0001] The present invention relates to a method for liquefying and manufacturing a propargyl carboxylate derivative used as a non-aqueous electrolyte additive for lithium secondary batteries, and to a liquid propargyl carboxylate composition produced thereby.

[0002] Lithium secondary batteries are generally manufactured by forming an electrode assembly by interposing a separator between a positive electrode including a positive electrode active material made of a transition metal oxide containing lithium and a negative electrode including a negative electrode active material capable of storing lithium ions, inserting the electrode assembly into a battery case, injecting a non-aqueous electrolyte that serves as a medium for transferring lithium ions, and then sealing the electrode assembly.

[0003] Lithium secondary batteries are miniaturized, boast high energy density, and high operating voltage, making them suitable for a wide range of applications, including mobile devices, electronic products, and electric vehicles. As the applications for lithium secondary batteries diversify, the physical properties required for them are also increasing. In particular, there is a growing demand for lithium secondary batteries that can operate stably even under high-temperature conditions.

[0004] Meanwhile, when a lithium secondary battery is operated under high temperature conditions, PF6 is generated from lithium salts such as LiPF6 contained in the electrolyte. - Anions can be thermally decomposed to generate Lewis acids such as PF5, which react with moisture to produce HF. These decomposition products such as PF5 and HF can not only destroy the film formed on the electrode surface, but also cause a decomposition reaction of the organic solvent. In addition, they can react with the decomposition products of the positive active material to elute transition metal ions, and the eluting transition metal ions can be deposited on the negative electrode, destroying the film formed on the negative electrode surface.

[0005] If the electrolyte decomposition reaction continues on the destroyed film in this way, the performance of the battery will further deteriorate, so the development of a secondary battery that can maintain excellent performance even under high-temperature conditions is required, and accordingly, a non-aqueous electrolyte that contains a specific combination of additives to help form the positive electrode film has been developed. As a method for manufacturing the above additive, there is a method of first reacting using two to three solvents, and then producing a solid additive through crystallization, filtration, and drying processes. This additive has the characteristic of being vulnerable to moisture and heat in a solid state, so in order to increase storage stability, it is dissolved again in a solvent at a certain composition and liquefied, and at this time, the non-aqueous electrolyte of the secondary battery is used as the solvent.

[0006] As the use of secondary batteries increases, the amount of additives used also increases, and liquefaction is continuously required for the purpose of additive storage stability and supply stability. However, environmental problems such as air emissions and disposal of organic solvents used in manufacturing may arise during the process of manufacturing additives by distilling away halogen solvents, and there is concern that problems such as increased processes and increased costs due to the need to re-dissolve additives in solvents after manufacturing, and the risk of quality deterioration due to exposure to external air and moisture may occur.

[0007] The present invention aims to simplify the manufacturing process of a propargyl carboxylate derivative, which is an additive for a non-aqueous electrolyte for a lithium secondary battery represented by the following chemical formula 3 or chemical formula 3A, and manufacture it in a liquid phase, thereby increasing the stability of a product that is vulnerable to moisture and heat stability due to being manufactured in a solid phase, and reducing costs, in order to solve the problems of the prior art.

[0008] [Chemical Formula 3]

[0009]

[0010] [Chemical Formula 3A]

[0011]

[0012] In addition, the present invention aims to solve environmental problems related to the disposal and atmospheric emission of solvents generated during the process by omitting the solidification process of the prior art, and to increase yield by preventing loss due to filtrate generated during the filtration process.

[0013] In order to solve the above technical problem, the present invention provides a method for producing a liquid phase of a propargyl carboxylate derivative as an electrolyte additive, comprising producing a compound in a starting material and a reaction organic solvent, washing the compound, and carrying out a moisture removal process to produce a product represented by chemical formula 3 in a liquid phase through three synthetic methods.

[0014] [Synthesis Method 1]

[0015] In one embodiment of the present invention, the method for producing a liquefied propargyl carboxylate derivative of the present invention comprises a raw material introduction step of introducing a starting material represented by the following chemical formula 1, a reaction organic solvent, and a compound represented by the following chemical formula 2; a reaction step of reacting the introduced raw materials while maintaining a temperature of 0 to 10°C to produce a reactant; a water washing step of washing the reactant with ultrapure water; and a moisture removal step of removing moisture from the washed reactant using a dehydrating agent; thereby producing a liquid product including a propargyl carboxylate derivative represented by the following chemical formula 3.

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1, R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0019] [Chemical Formula 2]

[0020]

[0021] In the above chemical formula 2, L1 may be an alkylene group having 1 to 3 carbon atoms.

[0022] [Chemical Formula 3]

[0023]

[0024] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, and L1 may be an alkylene group having 1 to 3 carbon atoms.

[0025] The compound represented by the above chemical formula 3 may be represented by the following chemical formula 3A.

[0026] [Chemical Formula 3A]

[0027]

[0028] In the above chemical formula 3A, L1 is an alkylene group having 1 to 3 carbon atoms, and R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0029] [Synthesis Method 2]

[0030] In one embodiment of the present invention, the method for producing a liquefied propargyl carboxylate derivative of the present invention comprises: a first raw material input step of introducing a starting material represented by the following chemical formula 4, a reaction organic solvent, and phosgene or triphosgene; a first reaction step of reacting the introduced raw materials by stirring at a temperature of 50 to 60° C. for 12 hours to produce a compound represented by the following chemical formula 1; a second raw material input step of introducing a compound represented by the following chemical formula 2 into the compound represented by the following chemical formula 1 produced in the first reaction step; a second reaction step of reacting the introduced raw materials to produce a reactant; a water washing step of washing the reactant with ultrapure water; and a moisture removal step of removing moisture from the washed reactant using a dehydrating agent; thereby producing a liquid product including a propargyl carboxylate derivative represented by the following chemical formula 3.

[0031] [Chemical Formula 1]

[0032]

[0033] In the above chemical formula 1, R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0034] [Chemical Formula 3]

[0035]

[0036] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, and L1 may be an alkylene group having 1 to 3 carbon atoms.

[0037] The compound represented by the above chemical formula 3 may be represented by the following chemical formula 3A.

[0038] [Chemical Formula 3A]

[0039]

[0040] In the above chemical formula 3A, L1 is an alkylene group having 1 to 3 carbon atoms, and R1 to R3 may each independently be hydrogen; or an alkyl group having 1 to 3 carbon atoms.

[0041] [Chemical Formula 4]

[0042]

[0043] In the above chemical formula 4, R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0044] [Synthesis Method 3]

[0045] In one embodiment of the present invention, the method for producing a liquefied propargyl carboxylate derivative of the present invention comprises: a first raw material input step of introducing a starting material represented by the following chemical formula 2, a reaction organic solvent, and phosgene or triphosgene; a first reaction step of reacting the introduced raw materials while maintaining a temperature of 20 to 30°C to produce a compound represented by the following chemical formula 5; a second raw material input step of introducing the compound represented by the chemical formula 5 produced in the first reaction step into a compound represented by the following chemical formula 4; a second reaction step of reacting the introduced raw materials to produce a reactant; a washing step of washing the reactant with ultrapure water; and a moisture removal step of removing moisture from the washed reactant using a dehydrating agent; thereby producing a liquid product including a propargyl carboxylate derivative represented by the following chemical formula 3.

[0046] [Chemical Formula 2]

[0047]

[0048] In the above chemical formula 2, L1 may be an alkylene group having 1 to 3 carbon atoms.

[0049] [Chemical Formula 3]

[0050]

[0051] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, and L1 may be an alkylene group having 1 to 3 carbon atoms.

[0052] The compound represented by the above chemical formula 3 may be represented by the following chemical formula 3A.

[0053] [Chemical Formula 3A]

[0054]

[0055] In the above chemical formula 3A, L1 is an alkylene group having 1 to 3 carbon atoms, and R1 to R3 may each independently be hydrogen; or an alkyl group having 1 to 3 carbon atoms.

[0056] [Chemical Formula 4]

[0057]

[0058] In the above chemical formula 1, R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0059] [Chemical Formula 5]

[0060]

[0061] In the above chemical formula 5, L1 may be an alkylene group having 1 to 3 carbon atoms.

[0062] In one embodiment of the present invention, the compound represented by chemical formula 3A may be propargyl 1H-imidazole-1-carboxylate.

[0063] In one embodiment of the present invention, the reaction organic solvent may include at least one selected from a cyclic carbonate solvent and a linear carbonate solvent.

[0064] In one embodiment of the present invention, the reaction organic solvent may additionally include a linear ester solvent and a cyclic ester solvent in addition to the cyclic carbonate solvent and the linear carbonate solvent.

[0065] In one embodiment of the present invention, the cyclic carbonate solvent may include at least one selected from ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and vinylene carbonate.

[0066] In one embodiment of the present invention, the linear carbonate solvent may include at least one selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate.

[0067] In one embodiment of the present invention, the solids content of the product may be 1 to 50%, more preferably 5 to 25%.

[0068] According to the present invention, since a separate solidification process for liquefying the product is unnecessary by producing a liquid product, the process of distilling and removing the solvent after the reaction and washing is also unnecessary, resulting in a cost reduction effect due to a reduction in the process.

[0069] Specifically, according to the present invention, by omitting the solidification process of the prior art, concerns about environmental issues regarding disposal and atmospheric emissions of solvents occurring in the crystallization step can be resolved, and losses due to filtrate occurring in the filtration process can be prevented, resulting in an effect of increasing the yield by approximately 10 to 15%.

[0070] Figure 1 shows a flow chart for Synthesis Method 1 among the liquefaction manufacturing methods of the propargyl carboxylate derivative of the present invention.

[0071] Figure 2 shows a flow chart for Synthesis Method 2 among the liquefaction manufacturing methods of the propargyl carboxylate derivative of the present invention.

[0072] Figure 3 shows a flow chart for Synthesis Method 3 among the liquefaction manufacturing methods of the propargyl carboxylate derivative of the present invention.

[0073] The present invention is a method for manufacturing an additive for a lithium secondary battery to improve the durability of a negative electrode, and is an invention that replaces a reaction organic solvent and a recrystallization solvent that must be removed after the reaction by improving reaction conditions.

[0074] The additive for a lithium secondary battery manufactured by the present invention is a substance that helps improve the durability of an anode. It is first reduced and decomposed at a relatively high anode potential to form a stable film, and the film thus formed is polymerized to improve the durability of the battery.

[0075] Specifically, since the compound represented by the above chemical formula 3 contains a propargyl functional group, when this functional group is reduced and decomposed, it forms an SEI film with high passivation ability on the surface of the negative electrode, which can not only improve the high-temperature durability of the negative electrode itself, but also prevent the electrodeposition of transition metals on the surface of the negative electrode. In addition, the propargyl group can adsorb onto the surface of metallic impurities included in the positive electrode, making it difficult for the impurities to be eluted, and thereby suppressing internal short circuits that may occur when the eluted metal ions are deposited on the negative electrode. Furthermore, since the propargyl group is easily reduced on the surface of the negative electrode, it can form a stable film on the surface of the negative electrode, thereby preventing self-discharge reactions of graphite-based and silicon-based negative electrodes caused by additional reduction and decomposition reactions of the electrolyte caused by the instability of the SEI film.

[0076] As an example, the method for manufacturing an additive for a lithium secondary battery of the present invention comprises: adding a starting material to a reaction organic solvent, reacting an alkynol dropwise to synthesize a product, and then washing and removing moisture to obtain a liquid product; the liquid product produced by the present invention can be packaged directly in a liquid form without going through a crystallization and filtration process.

[0077] The product of the present invention, propargyl 1H-imidazole-1-carboxylate, is susceptible to moisture and heat in a solid state. Therefore, to enhance storage stability, it can be liquefied using an electrolyte solvent to ensure stability. Accordingly, liquefaction is continuously required for the purpose of storage and supply stability.

[0078] Previously, the product was made into a solid and then dissolved in a diluted solvent used in the electrolyte. To make it into a solid, a filtration and drying process had to be performed after manufacturing.

[0079] In the present invention, a simplified manufacturing method for producing propargyl 1H-imidazole-1-carboxylate is described, which satisfies the liquefaction requirement by using a solvent used in an electrolyte as a reaction organic solvent without going through the conventional manufacturing, filtration, and drying processes.

[0080] [Synthesis Method 1]

[0081]

[0082] [Chemical Formula 1]

[0083]

[0084] In the above chemical formula 1, R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0085] [Chemical Formula 2]

[0086]

[0087] In the above chemical formula 2, L1 may be an alkylene group having 1 to 3 carbon atoms.

[0088] [Chemical Formula 3]

[0089]

[0090] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, and L1 may be an alkylene group having 1 to 3 carbon atoms.

[0091] The compound represented by the above chemical formula 3 may be represented by the following chemical formula 3A.

[0092] [Chemical Formula 3A]

[0093]

[0094] In the above chemical formula 3A, L1 is an alkylene group having 1 to 3 carbon atoms, and R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0095] The compound represented by the above chemical formula 3A may be propargyl 1H-imidazole-1-carboxylate.

[0096] After introducing a reaction organic solvent, a compound represented by Chemical Formula 1 (hereinafter referred to as a starting material), a compound represented by Chemical Formula 2 is added dropwise to react while maintaining a temperature of 0 to 10°C to synthesize a compound represented by Chemical Formula 3 (hereinafter referred to as a product). The compound represented by Chemical Formula 3 may be represented by Chemical Formula 3A below. The compound represented by Chemical Formula 3A may be propargyl 1H-imidazole-1-carboxylate. Among the starting materials, Chemical Formula 1 is used in an amount of 1 to 2 equivalents, preferably 1 to 1.2 equivalents. After synthesis, a water-washing and moisture-removing process is performed to obtain a liquid product.

[0097] Various organic solvents commonly used in lithium electrolytes can be used as the reaction organic solvent. For example, the reaction organic solvent can be a cyclic carbonate solvent, a linear carbonate solvent, or a mixture thereof, and preferably includes a cyclic carbonate solvent and a linear carbonate solvent.

[0098] The cyclic carbonate solvent is a high-viscosity organic solvent with a high dielectric constant, which can easily dissociate lithium salts in the electrolyte. Specifically, the cyclic carbonate solvent may be at least one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and vinylene carbonate, and preferably includes ethylene carbonate (EC).

[0099] In addition, the linear carbonate solvent is an organic solvent with excellent ionic conductivity and low viscosity and has a low dielectric constant. Specifically, it may be at least one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate, and ethyl propyl carbonate, and preferably includes ethyl methyl carbonate (EMC).

[0100] In addition, the above reaction organic solvent may additionally include a linear ester solvent and / or a cyclic ester solvent in addition to a cyclic carbonate solvent and / or a linear carbonate solvent.

[0101] These linear ester solvents may be one or more organic solvents specifically selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate and butyl propionate.

[0102] The cyclic ester solvent may be one or more organic solvents specifically selected from the group consisting of γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ-valerolactone, and ε-caprolactone.

[0103] Meanwhile, the above reaction organic solvent may be used by adding an organic solvent commonly used in electrolytes for lithium secondary batteries, if necessary. Specifically, one or more organic solvents among an ether solvent, an amide solvent, and a nitrile solvent may be additionally included.

[0104] The above product can be prepared in a liquid form having a solids content of 1 to 50%, more preferably 5 to 25%.

[0105] [Synthesis Method 2]

[0106]

[0107] [Chemical Formula 1]

[0108]

[0109] In the above chemical formula 1, R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0110] [Chemical Formula 2]

[0111]

[0112] In the above chemical formula 2, L1 may be an alkylene group having 1 to 3 carbon atoms.

[0113] [Chemical Formula 3]

[0114]

[0115] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, and L1 may be an alkylene group having 1 to 3 carbon atoms.

[0116] The compound represented by the above chemical formula 3A may be propargyl 1H-imidazole-1-carboxylate.

[0117] [Chemical Formula 4]

[0118]

[0119] In the above chemical formula 4, R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0120] After adding a reaction organic solvent, a compound represented by Chemical Formula 4 (hereinafter referred to as a starting material), and stirring the mixture with phosgene or triphosgene at a temperature of 50 to 60°C for 12 hours to synthesize a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2 is added dropwise to react to synthesize a compound represented by Chemical Formula 3 (hereinafter referred to as a product). The compound represented by Chemical Formula 3 may be represented by Chemical Formula 3A. The compound represented by Chemical Formula 3A may be propargyl 1H-imidazole-1-carboxylate.

[0121] Among the starting materials, the chemical formula 4 is 1 to 2 times the theoretical equivalent, preferably 1 to 1.2 times.

[0122] Afterwards, the product is washed and dehydrated to obtain a liquid product.

[0123] The same solvent as the reaction organic solvent of Synthesis Method 1 can be used as the reaction organic solvent.

[0124] The above product can be prepared in a liquid form having a solids content of 1 to 50%, more preferably 5 to 25%.

[0125] [Synthesis Method 3]

[0126]

[0127] [Chemical Formula 2]

[0128]

[0129] In the above chemical formula 2, L1 may be an alkylene group having 1 to 3 carbon atoms.

[0130] [Chemical Formula 3]

[0131]

[0132] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, and L1 may be an alkylene group having 1 to 3 carbon atoms.

[0133] The compound represented by the above chemical formula 3A may be propargyl 1H-imidazole-1-carboxylate.

[0134] [Chemical Formula 4]

[0135]

[0136] In the above chemical formula 4, R1 to R3 can each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0137] [Chemical Formula 5]

[0138]

[0139] In the above chemical formula 5, L1 may be an alkylene group having 1 to 3 carbon atoms.

[0140] After introducing a reaction organic solvent, a compound represented by Chemical Formula 2 (hereinafter referred to as a starting material), and reacting with phosgene or triphosgene while maintaining a temperature of 20 to 30°C, a compound represented by Chemical Formula 5 is synthesized, and then the compound represented by Chemical Formula 5 generated in the first reaction step is added dropwise to the compound represented by Chemical Formula 4 to synthesize a compound represented by Chemical Formula 3 (hereinafter referred to as a product). The compound represented by Chemical Formula 3 may be represented by Chemical Formula 3A.

[0141] Chemical formula 2 uses 1 times the theoretical equivalent, and phosgene or triphosgene is 1 to 2 times the theoretical equivalent, preferably 1 to 1.2 times.

[0142] The compound represented by chemical formula 3A may be propargyl 1H-imidazole-1-carboxylate. Afterwards, after washing and dewatering, the crystallization filtration process is omitted, and a liquid product is obtained.

[0143] The same solvent as the reaction organic solvent of Synthesis Method 1 can be used as the reaction organic solvent.

[0144] The above product can be prepared in a liquid form having a solids content of 1 to 50%, more preferably 5 to 25%.

[0145] Hereinafter, the present invention will be described in detail through specific examples.

[0146] <Example 1>

[0147] 100 g (0.617 mol) of 1,1'-carbonylbis-1H-imidazole and 500 g of ethyl methyl carbonate (EMC) were added and cooled to 0°C. After that, 33 g (0.586 mol) of 2-propyn-1-ol was added dropwise and the temperature of the reaction solution was maintained at 5°C.

[0148] After stirring for 60 minutes, the imidazole produced was filtered off and washed with ultrapure water.

[0149] After performing layer separation and adding magnesium sulfate to remove moisture, propargyl 1H-imidazole-1-carboxylate (hereinafter referred to as the product) dissolved in ethyl methyl carbonate was obtained, and the solid content of the product was 14%, the yield was 90 wt%, and the purity was 99.8%.

[0150] <Example 2>

[0151] The experiment was conducted under the same conditions as Example 1, except that dimethyl carbonate (DMC) was used as the reaction solvent.

[0152] The solid content of the product was 13%, the yield was 85 wt%, and the purity was 99.8%.

[0153] <Example 3>

[0154] The experiment was conducted under the same conditions as Example 1, except that a 1:1 mixed solution of ethyl methyl carbonate and dimethyl carbonate was used as the reaction solvent.

[0155] The solid content of the product was 14%, the yield was 88 wt%, and the purity was 99.8%.

[0156] <Example 4>

[0157] The experiment was conducted under the same conditions as Example 1, except that a 1:3 mixed solution of ethyl methyl carbonate and dimethyl carbonate was used as the reaction solvent.

[0158] The solid content of the product was 13%, the yield was 87 wt%, and the purity was 99.8%.

[0159] <Example 5>

[0160] The experiment was conducted under the same conditions as Example 1, except that a 3:1 mixed solution of ethyl methyl carbonate and dimethyl carbonate was used as the reaction solvent.

[0161] The solid content of the product was 14%, the yield was 89 wt%, and the purity was 99.8%.

[0162] <Example 6>

[0163] 100 g (1.47 mol) of imidazole and 500 g of ethyl methyl carbonate were added and cooled to 0°C. 43.6 g (0.147 mol) of triphosgene was dissolved in 200 g of ethyl methyl carbonate and added dropwise, maintained at 55°C, and stirred for 12 hours. After that, 23.5 g (0.42 mol) of 2-propyn-1-ol was added dropwise, and the temperature of the reaction solution was maintained at 5°C. After stirring for 60 minutes, the produced imidazole was removed by filtration and washed with ultrapure water. After layer separation and addition of magnesium sulfate to remove moisture, propargyl 1H-imidazole-1-carboxylate (hereinafter referred to as the product) dissolved in ethyl methyl carbonate was obtained, and the solid content of the product was 12%, the yield was 81 wt%, and the purity was 99.7%.

[0164] <Example 7>

[0165] Triphosgene 43.6 g (0.147 mol), activated carbon, and ethyl methyl carbonate 500 g were added and cooled to 0℃. After that, 2-propyn-1-ol 23.5 g (0.42 mol) was added dropwise, and the temperature of the reaction solution was raised to 25℃ and maintained. After stirring for 8 hours, the reaction solution was added dropwise to a reactor containing 100 g (1.47 mol) of imidazole and 300 g of ethyl methyl carbonate. After stirring for about 1 hour, the reaction was carried out, and then washed with ultrapure water. After layer separation and addition of magnesium sulfate to remove moisture, propargyl 1H-imidazole-1-carboxylate (hereinafter referred to as the product) dissolved in ethyl methyl carbonate was obtained. The solid content of the product was 12%, the yield was 80 wt%, and the purity was 99.7%.

[0166] <Reference Example 1>

[0167] The experiment was conducted under the same conditions as Example 1, except that dichloromethane was used as the reaction organic solvent, and a process of removing the solvent by distillation and a process of filtering the product were included.

[0168] The solid content of the product was 12%, the yield was 80 wt%, and the purity was 99.7%.

[0169] <Comparative Example 1>

[0170] The experiment was conducted under the same conditions as Example 1, except that the temperature of the reaction solution was set to 30°C.

[0171] The solid content of the product was 10%, the yield was 60 wt%, and the purity was 98.0%.

[0172] Comparative Example 2

[0173] The experiment was conducted under the same conditions as Example 6, except that dichloromethane was used as the reaction organic solvent, and a process of removing the solvent by distillation and a process of filtering the product were included.

[0174] The solid content of the product was 12%, the yield was 74 wt%, and the purity was 99.7%.

[0175] <Comparative Example 3>

[0176] The experiment was conducted under the same conditions as Example 7, except that dichloromethane was used as the reaction organic solvent, and a process of removing the solvent by distillation and a process of filtering the product were included.

[0177] The solid content of the product was 12%, the yield was 73 wt%, and the purity was 99.6%.

[0178] Reaction organic solvent product filtration Whether waste organic solvent is generated Reaction temperature Solid content (%) Yield Purity Suitability (O / X) (℃) (weight %) (%) Compliance standard X Compliance standard 1~50% Compliance standard 80% or more Compliance standard 99.0% or more Example 1 EMCXX 5149099.8O Example 2 DMCXX 5138599.8O Example 3 EMC:DMC = 1:1XX 5148899.8O Example 4 EMC:DMC = 1:3XX 5138799.8O Example 5 EMC:DMC = 3:1XX5148999.8OExample 6EMCXX5128199.7OExample 7EMCXX5128099.7OReference Example 1DichloromethaneOO5128099.7XComparative Example 1EMCXX30106098.0XComparative Example 2DichloromethaneOO5127499.7XComparative Example 3DichloromethaneOO5127399.6X

[0179] It is suitable when the solid content of the product is 1 to 50% (more preferably 5 to 25%), the yield is 80% or more, and the purity is 99.5% or more. The products produced by the methods of Examples 1 to 7 show a yield of 80 to 90 wt%, which is the same as or about 13 wt% higher than the yield of 80 wt% of Reference Example 1. This is because the carbonate solvent used as the electrolyte solvent is used as the reaction organic solvent, so that the distillation removal process, crystallization process, and filtration process of the solvent in the manufacturing process become unnecessary, and accordingly, by omitting the use of additional solvent, the amount that may be lost due to each process is not lost and is preserved. In addition, since the product is not filtered, it can be confirmed that waste organic solvent is not generated due to the filtrate. When using other organic solvents as reaction organic solvents, the product must be made into a solid and then diluted again with a carbonate solvent, so an increase in yield is also advantageous in terms of process cost. In Reference Example 1, Comparative Example 2, and Comparative Example 3, dichloromethane was used as the reaction organic solvent, and since a process of removing the solvent by distillation is required, a product filtration process is performed, and it can be confirmed that waste organic solvent is generated accordingly.

[0180] Dichloromethane is a hazardous substance, and its distillation after the reaction can cause environmental problems. Furthermore, the additional use of ethyl acetate and hexane during the crystallization of the product increases production costs. Furthermore, the disposal of the filtrate, a mixed solvent of ethyl acetate and hexane, after the filtration process also poses environmental problems. Even if distilled, the filtrate cannot be reused due to the mixture of ethyl acetate, hexane, and the reaction organic solvent, dichloromethane, which causes environmental problems and increases the unit cost of the process.

[0181] The present invention improves reaction conditions to replace the reaction organic solvent and recrystallization solvent that must be removed after the reaction. Since the hazardous substance dichloromethane is not used, the process of distilling and removing the solvent after the reaction is unnecessary, eliminating concerns about the resulting environmental problems. Furthermore, since the crystallization process for the product is unnecessary, the use of a mixed solvent of ethyl acetate and hexane is also unnecessary, eliminating the generation of waste organic solvents and eliminating environmental pollution issues related to solvent disposal or the cost issues associated with solvent use.

[0182] <Advantages of liquid composition>

[0183] <Comparative Test Example 1>

[0184] The stability of solid propargyl 1H-imidazole-1-carboxylate and propargyl 1H-imidazole-1-carboxylate (initial purity 99.8%) was confirmed by storing them at 5℃.

[0185] The purity of the product was 99.6% after one week and 98.2% after one month.

[0186] <Comparative Test Example 2>

[0187] The experiment was conducted under the same conditions as Comparative Test Example 1, except that the solids content was 60%.

[0188] The product had some precipitated solids, and the purity of the product was 99.6% after one week and 98.5% after one month.

[0189] <Example 1>

[0190] The products synthesized with a solid content of 5% using solid propargyl 1H-imidazole-1-carboxylate and propargyl 1H-imidazole-1-carboxylate (initial purity 99.8%) and ethyl methyl carbonate as a reaction solvent were stored at 5℃ and their stability was confirmed.

[0191] The purity of the product was 99.8% after one week and 99.8% after one month.

[0192] <Example 2>

[0193] The experiment was conducted under the same conditions as Test Example 1, except that the solids content was 50%.

[0194] The purity of the product was 99.8% after one week and 99.8% after one month.

[0195] Reaction Solvent Solid Content (%)Storage TemperaturePurity after 1 weekPurity after 1 monthAppropriate (O / X)(℃)(%)(%)Compliance Criteria 99.0% or moreCompliance Criteria 99.0% or moreTest Example 1 Ethyl Methyl Carbonate 5599.899.8OTest Example 2 Ethyl Methyl Carbonate 50599.899.8OComparative Test Example 1 N / A 100599.698.2XComparative Test Example 2 Ethyl Methyl Carbonate 60599.698.5X

[0196] The product is stable when stored at a temperature of 10℃ or lower, preferably 5℃ or lower, and when stored using the solid content method of Comparative Test Example 1 and Comparative Test Example 2 in which the solid content exceeds 50%, the product's storage stability can be improved when the solid content is 1 to 50%, more preferably 5 to 25%, as in Test Examples 1 and 2. In addition, by dissolving and storing in a carbonate solvent used as an electrolyte solvent, there is no dust generation during use, making it easy to use, and it can be used without any loss of the product that may stick to the wall of the storage container.

Claims

1. A raw material input step of inputting a starting material represented by the following chemical formula 1, a reaction organic solvent, and a compound represented by the following chemical formula 2; A reaction step of generating a reactant by reacting the above-mentioned raw materials while maintaining a temperature of 0 to 10°C; A washing step of washing the above reactants with ultrapure water; and A method for producing a liquid product comprising a propargyl carboxylate derivative represented by the following chemical formula 3, including a moisture removal step of removing moisture from the washed reactant using a dehydrating agent. [Chemical Formula 1] In the above chemical formula 1, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, [Chemical Formula 2] In the above chemical formula 2, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 3] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, L1 is an alkylene group having 1 to 3 carbon atoms.

2. A first raw material input step of inputting a starting material represented by the following chemical formula 4, a reaction organic solvent, and phosgene or triphosgene; A first reaction step of reacting the above-mentioned raw materials by stirring them for 12 hours while maintaining a temperature of 50 to 60°C to produce a compound represented by the following chemical formula 1; A second raw material input step of inputting a compound represented by the following chemical formula 2 into a compound represented by the following chemical formula 1 produced in the first reaction step; A second reaction step of generating a reactant by reacting the above-mentioned raw materials while maintaining a temperature of 0 to 10°C; A washing step of washing the above reactants with ultrapure water; and A method for producing a liquid product comprising a propargyl carboxylate derivative represented by the following chemical formula 3, including a moisture removal step of removing moisture from the washed reactant using a dehydrating agent. [Chemical Formula 1] In the above chemical formula 1, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, [Chemical Formula 2] In the above chemical formula 2, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 3] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 4] In the above chemical formula 4, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.

3. A first raw material input step of inputting a starting material represented by the following chemical formula 2, a reaction organic solvent, and phosgene or triphosgene; A first reaction step of producing a compound represented by the following chemical formula 5 by reacting the above-mentioned raw materials while maintaining a temperature of 20 to 30°C; A second raw material input step of inputting a compound represented by chemical formula 5 generated in the first reaction step into a compound represented by chemical formula 4; A second reaction step of generating a reactant by reacting the above-mentioned raw materials; A washing step of washing the above reactants with ultrapure water; and A method for producing a liquid product comprising a propargyl carboxylate derivative represented by the following chemical formula 3, including a moisture removal step of removing moisture from the washed reactant using a dehydrating agent. [Chemical Formula 2] In the above chemical formula 2, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 3] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 4] In the above chemical formula 4, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, [Chemical Formula 5] In the above chemical formula 5, L1 is an alkylene group having 1 to 3 carbon atoms.

4. In any one of paragraphs 1 to 3, A method for producing a liquefied propargylcarboxylate derivative, wherein the compound represented by the above chemical formula 3 is represented by the following chemical formula 3A. [Chemical Formula 3A] In the above chemical formula 3A, L1 is an alkylene group having 1 to 3 carbon atoms, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.

5. In any one of paragraphs 1 to 3, A method for producing a liquefied propargyl carboxylate derivative, wherein the compound represented by the above chemical formula 3 is propargyl 1H-imidazole-1-carboxylate.

6. In any one of paragraphs 1 to 3, A method for producing a liquefied propargyl carboxylate derivative, wherein the above reaction organic solvent comprises at least one selected from a cyclic carbonate solvent and a linear carbonate solvent.

7. In paragraph 6, A method for producing a liquefied propargyl carboxylate derivative, wherein the cyclic carbonate solvent comprises at least one selected from ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and vinylene carbonate.

8. In paragraph 6, A method for producing a liquefied propargyl carboxylate derivative, wherein the linear carbonate solvent comprises at least one selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate.

9. In any one of paragraphs 1 to 3, The above product is a method for producing a liquefied propargylcarboxylate derivative having a solid content of 1 to 50%.

10. Starting material represented by the following chemical formula 1; Reactive organic solvent; and Using the compound represented by chemical formula 2 as a raw material, A liquid propargylcarboxylate derivative composition having a solid content of 1 to 50% represented by the following chemical formula 3, produced through the synthetic method of claim 1. [Chemical Formula 1] In the above chemical formula 1, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, [Chemical Formula 2] In the above chemical formula 2, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 3] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, L1 is an alkylene group having 1 to 3 carbon atoms.

11. A substance represented by the following chemical formula 4; Reactive organic solvent; and Phosgene or triphosgene as a starting material; A liquid propargylcarboxylate derivative composition having a solid content of 1 to 50% represented by the following chemical formula 3, produced through the synthetic method of the second clause. [Chemical Formula 1] In the above chemical formula 1, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, [Chemical Formula 2] In the above chemical formula 2, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 3] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 4] In the above chemical formula 4, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.

12. A substance represented by the following chemical formula 2; Reactive organic solvent; and Starting with phosgene or triphosgene A liquid propargylcarboxylate derivative composition having a solid content of 1 to 50% represented by the following chemical formula 3, produced through the synthetic method of Article 3. [Chemical Formula 2] In the above chemical formula 2, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 3] In the above chemical formula 3, Ar is a 5 to 6-membered heteroaromatic ring containing at least one N, L1 is an alkylene group having 1 to 3 carbon atoms, [Chemical Formula 4] In the above chemical formula 4, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, [Chemical Formula 5] In the above chemical formula 5, L1 is an alkylene group having 1 to 3 carbon atoms.

13. In any one of paragraphs 10 to 12, A liquid propargylcarboxylate derivative composition, wherein the compound represented by the above chemical formula 3 is represented by the following chemical formula 3A. [Chemical Formula 3A] In the above chemical formula 3A, L1 is an alkylene group having 1 to 3 carbon atoms, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.

14. In any one of paragraphs 10 to 12, A liquid propargyl carboxylate derivative composition in which the compound represented by the above chemical formula 3 is propargyl 1H-imidazole-1-carboxylate.

15. In any one of paragraphs 10 to 12, The above product is a liquid propargylcarboxylate derivative composition having a solid content of 5 to 25%.

Images