Method for preparing n-vinyl-2-pyrrolidone intermediate and n-vinyl-2-pyrrolidone intermediate prepared therefrom

Abstract

The present invention relates to a method for preparing an N-vinyl-2-pyrrolidone intermediate, to an N-vinyl-2-pyrrolidone intermediate prepared by the preparation method, and to N-vinyl-2-pyrrolidone prepared from the N-vinyl-2-pyrrolidone intermediate. The preparation method comprises the steps of: (1) preparing a reactant containing a polyhydroxyalkanoate obtained by microbial cultivation; and (2) reacting the reactant containing the polyhydroxyalkanoate with an amine compound at a temperature exceeding 200 ℃ so as to produce an intermediate-containing product.

Description

Method for preparing N-vinyl-2-pyrrolidone intermediate and N-vinyl-2-pyrrolidone intermediate prepared therefrom

[0001] The present invention relates to a method for producing an intermediate (precursor) used in producing N-vinyl-2-pyrrolidone (NVP), a high value-added chemical, in high yield.

[0002] Biorefinery is a technology that produces biofuels (energy), electricity, heat, and high value-added chemicals from biomass through biological or chemical conversion processes.

[0003] Recently, technologies have been developed to chemically depolymerize polyhydroxyalkanoate (PHA), one of the aforementioned biomass products, to produce high-value-added chemicals or intermediates. One example is the production of N-vinyl-2-pyrrolidone (NVP) intermediates or N-vinyl-2-pyrrolidone (NVP) using PHA.

[0004] The above NVP intermediate is a raw material used in manufacturing NVP, a high value-added chemical substance, and an improvement in its yield can lead to an improvement in the productivity of NVP.

[0005] Traditionally, NVP intermediates, or NVP, were produced by obtaining 1,4-butanediol (1,4-BDO) from petrochemical-derived acetylene, converting it to γ-butyrolactone (GBL), and then producing 2-pyrrolidone, N-vinyl-2-pyrrolidone (NVP), etc. However, this production method has long reaction steps and increases the unit price of NVP due to the use of expensive metal catalysts.

[0006] Meanwhile, the production of NVP intermediates or NVP using the above polyhydroxyalkanoates also has long and complex reaction steps, and the yields of NVP intermediates and NVP do not show satisfactory levels.

[0007] As described above, conventional methods for producing NVP intermediates, or NVP in an environmentally friendly, economical, and high-yield manner, have been limited. Specifically, using biomass polyhydroxyalkanoates to produce NVP intermediates can address environmental concerns and the depletion of petroleum resources. However, this method suffers from lengthy and complex reaction steps and significantly lower yields of NVP intermediates.

[0008] Accordingly, the inventors of the present invention have conducted various studies to solve the above problem, and as a result, they have confirmed that an N-vinyl-2-pyrrolidone (NVP) intermediate can be produced in high yield through relatively simple reaction steps by controlling the composition of the reactant including polyhydroxyalkanoate, the reaction temperature of the reactant, etc.

[0009] Accordingly, the object of the present invention is to provide a method for producing an N-vinyl-2-pyrrolidone (NVP) intermediate, which can produce the N-vinyl-2-pyrrolidone (NVP) intermediate in high yield through simple reaction steps using a reactant containing polyhydroxyalkanoate.

[0010] In addition, another object of the present invention is to provide an N-vinyl-2-pyrrolidone (NVP) intermediate manufactured by the above manufacturing method and N-vinyl-2-pyrrolidone (NVP) manufactured using the same.

[0011] To achieve the above object, the present invention provides a method for producing an N-vinyl-2-pyrrolidone intermediate, comprising the steps of: (1) preparing a reactant comprising polyhydroxyalkanoate obtained through microbial culture; and (2) reacting the reactant comprising the polyhydroxyalkanoate with an amine compound at a temperature exceeding 200°C to produce a product containing the intermediate.

[0012] According to one embodiment of the present invention, in the step (1), the polyhydroxyalkanoate may include a repeating unit derived from 4-hydroxybutyrate.

[0013] According to another embodiment of the present invention, the content of the polyhydroxyalkanoate included in the reactant in the step (1) may be 60 wt% to 90 wt% based on the total weight of the reactant.

[0014] According to another embodiment of the present invention, in the step (1), the moisture content of the reactant may be 0 wt% to 80 wt% based on the total weight of the reactant.

[0015] According to another embodiment of the present invention, in step (1), the reactant may additionally include an inorganic substance.

[0016] According to another embodiment of the present invention, the content of the inorganic material may be from more than 0 wt% to 10 wt% based on the total weight of the reactants.

[0017] According to another embodiment of the present invention, the inorganic material may include at least one selected from the group consisting of calcium carbonate (CaCO3), ferric sulfate (Fe2(SO4)3), and sodium bicarbonate (NaHCO3).

[0018] According to another embodiment of the present invention, the initial reaction pressure of the reactant and the amine compound in step (2) may be 1 bar to 120 bar.

[0019] According to another embodiment of the present invention, in the step (2), the amine compound may include a compound selected from the group consisting of monoethanolamine, monoethanolamine aqueous solution, ammonia, ammonia water, urea, and urea water.

[0020] According to another embodiment of the present invention, in step (2), the reactant and the amine compound can react at an equivalent ratio of 1:1.1 to 3.

[0021] According to another embodiment of the present invention, in the step (2), the intermediate may be N-(2-hydroxyethyl)-2-pyrrolidone.

[0022] Meanwhile, the present invention provides an N-vinyl-2-pyrrolidone intermediate manufactured by the method for manufacturing the N-vinyl-2-pyrrolidone intermediate.

[0023] In addition, the present invention provides N-vinyl-2-pyrrolidone prepared from the above N-vinyl-2-pyrrolidone intermediate.

[0024] In addition, the present invention provides a method for producing N-vinyl-2-pyrrolidone, comprising the steps of reacting an N-vinyl-2-pyrrolidone intermediate produced by the method for producing the N-vinyl-2-pyrrolidone intermediate and acetic anhydride to obtain an acetic acid ester intermediate; and the step of deacetating the obtained acetic acid ester intermediate.

[0025] In addition, the present invention provides a method for producing N-vinyl-2-pyrrolidone, which comprises a step of intramolecularly dehydrating an N-vinyl-2-pyrrolidone intermediate produced by the method for producing the N-vinyl-2-pyrrolidone intermediate in the presence of a catalyst.

[0026] The present invention produces an N-vinyl-2-pyrrolidone intermediate (N-vinyl-2-pyrrolidone precursor) through a relatively simple (short) reaction step compared to the conventional method without using a metal catalyst, thereby producing an N-vinyl-2-pyrrolidone intermediate in high yield and at low cost.

[0027] Furthermore, the present invention can increase the production amount of N-vinyl-2-pyrrolidone manufactured using the N-vinyl-2-pyrrolidone intermediate by increasing the yield of the N-vinyl-2-pyrrolidone intermediate, thereby contributing to providing N-vinyl-2-pyrrolidone, a raw material for the synthesis of polyvinylpyrrolidone (PVP), which is widely used in the manufacture of cosmetics, foods, pharmaceuticals, paper, fibers, pigments, paints, electronic devices, etc., with high efficiency.

[0028] Figure 1 is a flow chart showing a process for manufacturing an N-vinyl-2-pyrrolidone intermediate according to one embodiment of the present invention.

[0029] Figure 2 is a graph showing the results according to Test Example 1.

[0030] Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the contents disclosed below, and may be modified in various forms as long as the gist of the invention is not changed.

[0031] The word "comprising" or "including" in this specification is intended to specify particular features, regions, steps, processes, elements and / or components, and does not exclude the presence or addition of other features, regions, steps, processes, elements and / or components, unless specifically stated to the contrary.

[0032] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification are understood to be modified by the term “about” in all cases unless otherwise specified.

[0033]

[0034] The present invention provides a method for producing an N-vinyl-2-pyrrolidone intermediate using biomass polyhydroxyalkanoate, an N-vinyl-2-pyrrolidone intermediate produced by the method, N-vinyl-2-pyrrolidone produced from the N-vinyl-2-pyrrolidone intermediate, and a method for producing the same. The present invention has the characteristic of being able to produce an N-vinyl-2-pyrrolidone intermediate in a high yield through a simple reaction step without using an expensive metal catalyst by optimizing the composition of a reactant including polyhydroxyalkanoate (e.g., components of the reactant, moisture content of the reactant, etc.) and the reaction temperature of the reactant, and this is specifically described as follows.

[0035]

[0036] Method for preparing N-vinyl-2-pyrrolidone intermediate

[0037] The method for producing an N-vinyl-2-pyrrolidone intermediate (hereinafter referred to as “NVP intermediate”) according to the present invention comprises the steps of (1) preparing a reactant containing polyhydroxyalkanoate obtained through microbial culture; and (2) reacting the reactant containing the polyhydroxyalkanoate with an amine compound at a temperature exceeding 200°C to produce a product containing the intermediate, which will be described below with reference to FIG. 1.

[0038]

[0039] Step (1): Preparation of reactants

[0040] According to the present invention, step (1) is a step (S (1)) of preparing a reactant containing polyhydroxyalkanoate obtained through microbial culture.

[0041] The above reactant is not particularly limited as long as it is a substance containing polyhydroxyalkanoate. Specifically, the reactant is a substance obtained from a cell fermentation culture medium containing polyhydroxyalkanoate, and may include polyhydroxyalkanoate, cell, cell-derived material, and debris. In addition, the reactant may be polyhydroxyalkanoate itself obtained through a process of separating and purifying a substance obtained from the cell fermentation culture medium using a conventional method.

[0042] For example, the reactant may be a dried cell material obtained by adding a polymer coagulant and water (e.g., distilled water) to a cell fermentation culture containing polyhydroxyalkanoate to obtain a cell aggregate, and dehydrating the obtained cell aggregate. In addition, the reactant may be a cell fermentation culture that has not undergone the coagulation and dehydration, or a cell aggregate (or cell aggregate) that has not undergone the dehydration after the coagulation. The cell fermentation culture or the cell aggregate (or cell aggregate) has not undergone a purification process (e.g., a dehydration process), and by applying it as a reactant, the manufacturing process of the NVP intermediate can be shortened while reducing the cost consumed in the purification process, thereby making it possible to economically manufacture the NVP intermediate and / or NVP.

[0043] The above-mentioned fungal fermentation culture solution may be obtained by culturing a microorganism having the ability to produce biomass containing polyhydroxyalkanoate. The above microorganisms are Bacillus subtilis, Cupriavidus necator, Bacillus cereus, Bacillus brevis, Caulobacter cresentus, Bacillus sphaericus, Bacillus coagulans, Bacillus megaterium, Bacilllus circulands, Bacillus licheniformis, Escherichia coli, Microlanatus phosphovorous, Rhizobium meliloti, Rhizobium viciae, and Bradyrhizobium. Bredyrhizobium japonicum, Burkholderia cepacia, Burkholderia sacchari, Cupriavidus necactor, Neptunamonas Antarctica, Azobacter vinelandii, Pseudomonas putida, Pseudomonas aeruginosa, Aeromonas caviae, Aeromonas hydrophila, Aeromonas punctate, Alcaligenes latus, Halomonas boliviensis,It may include, but is not limited to, one or more species selected from the group consisting of Lactobacillus rhamnosus and Firmicutes bacterium.

[0044] The polymer coagulant may not be particularly limited as long as it is a polymer substance capable of coagulating the fungal fermentation culture medium. Specifically, the polymer coagulant may include a cationic polymer coagulant having a molecular weight of 1,000,000 Da or more (e.g., 1,000,000 Da to 10,000,000 Da, 1,000,000 Da to 5,000,000 Da, 1,300,000 Da to 4,500,000 Da, 1,500,000 Da to 4,000,000 Da, 2,000,000 Da to 3,500,000 Da, 2,300,000 Da to 3,000,000 Da, or 2,500,000 Da to 3,000,000 Da). For example, the polymer flocculant may be a polymer flocculant solution in which the cationic polymer flocculant is dissolved or dispersed in a solvent (e.g., distilled water). Since the polymer flocculant includes the cationic polymer flocculant, the flocculation efficiency of a cell fermentation culture solution containing an anionic polyhydroxyalkanoate can be significantly increased.

[0045] For example, the cationic polymer coagulant may be a coagulant including an acrylamide-based polymer, an acryloyl-based polymer, an amidine-based polymer, a polyvinylamine-based polymer, a diallyldimethylammonium chloride-based polymer, a polyamine-based polymer, or a combination thereof, and specifically, may be a polyacrylamide-based polymer coagulant.

[0046] Dehydration of the above-mentioned fungal aggregate liquid can be performed using at least one of a press and an electroosmotic dehydrator, but is not limited thereto. Specifically, the fungal aggregate liquid can be first dehydrated using a press to obtain an aggregate, and then secondarily dehydrated using the electroosmotic dehydrator to obtain a reactant (dried fungal material). By performing this dehydration, the present invention can control the moisture content of the reactant as desired while minimizing the content of impurities contained in the reactant.

[0047] The above press is not particularly limited as long as it is a commonly known press, and specifically may be a screw press, a wedge press, a hydraulic press, etc.

[0048] The operating pressure of the press (e.g., the operating pressure of the pressing plate provided in the press) is not particularly limited, but may be 0.01 MPa to 1 MPa. Specifically, the operating pressure of the press may be 0.03 MPa to 0.9 MPa, 0.05 MPa to 0.7 MPa, 0.1 MPa to 0.6 MPa, 0.2 MPa to 0.5 MPa, or 0.3 MPa to 0.4 MPa, but is not limited thereto. When the operating pressure of the press is within the above range, primary dehydration can be efficiently performed while preventing damage to the polyhydroxyalkanoate.

[0049] The above-mentioned electroosmotic dehydrator may not be particularly limited as long as it is a dehydrator that applies the electrophoresis principle.

[0050] The operating conditions of the electroosmotic dehydrator are not particularly limited, but the operating speed may be 0.1 m / min to 4 m / min, and the applied voltage may be 10 V to 150 V. Specifically, the operating speed of the electroosmotic dehydrator may be 0.5 m / min to 3.5 m / min, 0.7 m / min to 3 m / min, 0.9 m / min to 2.5 m / min, 1 m / min to 2 m / min, or 1.1 m / min to 1.5 m / min, and the applied voltage of the electroosmotic dehydrator may be, but is not limited to, 12 V to 130 V, 13 V to 100 V, 15 V to 50 V, 17 V to 30 V, or 19 V to 25 V. When the operating conditions of the electroosmotic dehydrator are within the above range, secondary dehydration and impurity removal can be efficiently performed.

[0051] Meanwhile, in order to promote the fluidity and chemical reactivity of the above-mentioned fungal cell agglomerate, an inorganic substance may be further added to the above-mentioned fungal cell fermentation culture liquid together with the above-mentioned polymer agglomerate. Accordingly, the reactant obtained through the above-mentioned agglomeration and / or the above-mentioned dehydration may additionally contain an inorganic substance.

[0052] According to the present invention, the content of the inorganic matter additionally included in the reactant may be more than 0 wt% to 10 wt% based on the total weight of the reactant (e.g., a reactant having a moisture content of 0 wt%). Specifically, the inorganic matter content of the reactant may be 0.1 wt% to 9.8 wt%, 0.3 wt% to 9.5 wt%, 0.5 wt% to 9 wt%, 1 wt% to 8 wt%, 1.5 wt% to 7 wt%, 2 wt% to 6.5 wt%, 2.5 wt% to 6 wt%, 3 wt% to 5.5 wt%, 3.5 wt% to 5 wt%, or 4 wt% to 5 wt%, based on the total weight of the reactant, but is not limited thereto. When the inorganic matter content of the reactant is within the above range, the fluidity and chemical reactivity of the reactant can be optimized.

[0053] Considering the fluidity and chemical reactivity of the reactants, the inorganic material may include at least one selected from the group consisting of calcium carbonate (CaCO3), ferric sulfate (Fe2(SO4)3), and sodium bicarbonate (NaHCO3), but is not limited thereto. For example, the inorganic material may include all of calcium carbonate (CaCO3), ferric sulfate (Fe2(SO4)3), and sodium bicarbonate (NaHCO3).

[0054] According to the present invention, the moisture content of the reactant can be controlled to increase the yield of the NVP intermediate. For example, the reactant obtained through the coagulation and dehydration can have a moisture content of 0 wt%, and the moisture content of the reactant can be controlled by performing a step of adding water (e.g., distilled water) to the reactant having a moisture content of 0 wt%. In addition, the reactant can be a cell fermentation culture solution that has not undergone the coagulation and dehydration, and thus the moisture content can be controlled by including moisture derived from the cell fermentation culture solution. In addition, the reactant can be a cell aggregate solution (or cell aggregate) that has not undergone the dehydration after the coagulation, and thus the moisture content can be controlled by including moisture derived from the cell fermentation culture solution and the cell aggregate solution (or cell aggregate).

[0055] Specifically, the moisture content included in the reactant may be 0 wt% to 80 wt% based on the total weight of the reactant. More specifically, the moisture content of the reactant may be 5 wt% to 80 wt%, 10 wt% to 79 wt%, 15 wt% to 78 wt%, 20 wt% to 77 wt%, 25 wt% to 76 wt%, 30 wt% to 75 wt%, 35 wt% to 74 wt%, 40 wt% to 73 wt%, 45 wt% to 72 wt%, 50 wt% to 71 wt%, or 55 wt% to 70 wt% based on the total weight of the reactant, but is not limited thereto. When the moisture content of the reactant is within the above range, the conversion rate of polyhydroxyalkanoate is maximized, thereby significantly increasing the yield of the NVP intermediate.

[0056] Meanwhile, the polyhydroxyalkanoate (PHA) included in the above reactant is a thermoplastic natural polyester polymer that accumulates within the cells of microorganisms, and has properties similar to synthetic biodegradable resins such as polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST), and polybutylene succinate adipate (PBSA) derived from petroleum, while having excellent biodegradability and biocompatibility.

[0057] These polyhydroxyalkanoates may have a weight average molecular weight (Mw) of, but is not limited to, 100,000 g / mol to 1,000,000 g / mol, 200,000 g / mol to 900,000 g / mol, 300,000 g / mol to 800,000 g / mol, 400,000 g / mol to 700,000 g / mol, or 500,000 g / mol to 600,000 g / mol.

[0058] The above polyhydroxyalkanoate may include repeating units derived from at least one selected from the group consisting of 3-hydroxybutyrate (3HB), 3-hydroxypropionate (3HP), 3-hydroxyhexanoate (3HH), 3-hydroxyvalerate (3HV), 4-hydroxybutyrate (4HB), 4-hydroxyvalerate (4HV), 5-hydroxyvalerate (5HV), and 6-hydroxyhexanoate (6HH) (from at least one monomer).

[0059] Specifically, the polyhydroxyalkanoate may be a homopolymer comprising repeating units derived from 3-hydroxybutyrate (3HB) or repeating units derived from 4-hydroxybutyrate (4HB). Furthermore, the polyhydroxyalkanoate may be a copolymer comprising repeating units derived from 3-hydroxybutyrate (3HB) and repeating units derived from 4-hydroxybutyrate (4HB).

[0060] Preferably, the polyhydroxyalkanoate may be a single polymer (e.g., poly-4-hydroxybutyrate (P4HB)) comprising repeating units derived from 4-hydroxybutyrate (4HB). Since the polyhydroxyalkanoate comprises repeating units derived from 4-hydroxybutyrate (4HB), the reaction with the amine compound described below at high temperature is optimized, thereby increasing the yield of the NVP intermediate.

[0061] According to the present invention, the content of the polyhydroxyalkanoate included in the reactant may be 60 wt% to 90 wt% based on the total weight of the reactant (e.g., a reactant having a moisture content of 0 wt%). Specifically, the polyhydroxyalkanoate content of the reactant may be 63 wt% to 90 wt%, 65 wt% to 89 wt%, 68 wt% to 88 wt%, 70 wt% to 86 wt%, 73 wt% to 85 wt%, 75 wt% to 83 wt%, 76 wt% to 82 wt%, or 78 wt% to 80 wt%, based on the total weight of the reactant, but is not limited thereto. When the polyhydroxyalkanoate content of the reactant is within the above range, the yield of the NVP intermediate can be increased.

[0062]

[0063] Step (2): Production of intermediate-containing products

[0064] According to the present invention, step (2) is a step (S (2)) of producing an intermediate-containing product by reacting a reactant including the polyhydroxyalkanoate and an amine compound at a temperature exceeding 200°C.

[0065] The reaction temperature of the above reactant and the amine compound is not particularly limited as long as it exceeds 200°C. Specifically, the reaction temperature may be 205°C or higher, 210°C or higher, 215°C or higher, 220°C or higher, 225°C or higher, 230°C or higher, 235°C or higher, 240°C or higher, 245°C or higher, or 250°C or higher, and may be 350°C or lower, 340°C or lower, 330°C or lower, 320°C or lower, 310°C or lower, 300°C or lower, 290°C or lower, 280°C or lower, 270°C or lower, 260°C or lower, or 250°C or lower, but is not limited thereto. For example, the reaction temperature may be 210°C to 350°C, 220°C to 330°C, 230°C to 310°C, 240°C to 290°C, or 250°C to 270°C.

[0066] According to the present invention, the initial reaction pressure (initial set pressure for the reaction to proceed) of the reactants and the amine compound may be 1 bar to 120 bar. Specifically, the initial reaction pressure may be 1 bar to 115 bar, 3 bar to 110 bar, 5 bar to 105 bar, 7 bar to 100 bar, 10 bar to 90 bar, 15 bar to 85 bar, 20 bar to 80 bar, 25 bar to 75 bar, 30 bar to 70 bar, 35 bar to 65 bar, 40 bar to 60 bar, or 50 bar to 55 bar, but is not limited thereto.

[0067] As the above reaction temperature and the above initial reaction pressure are each within the above range, the conversion rate of the polyhydroxyalkanoate included in the reactant into the intermediate (e.g., N-(2-hydroxyethyl)-2-pyrrolidone) desired in the present invention can be significantly increased, thereby enabling the NVP intermediate to be produced in high yield through a simple reaction step.

[0068] Meanwhile, after the reaction of the above reactant and the above amine compound is carried out for 30 minutes, the pressure measured during the reaction is not particularly limited, but may be 10 bar to 150 bar, 15 bar to 140 bar, 18 bar to 130 bar, 20 bar to 120 bar, 25 bar to 110 bar, 30 bar to 100 bar, 40 bar to 90 bar, or 50 bar to 80 bar.

[0069] In addition, the reaction time of the above reactant and the amine compound is not particularly limited, but considering the yield of the NVP intermediate, it may be 1 hour to 10 hours, 1.5 hours to 8 hours, 2 hours to 6 hours, 2.5 hours to 5 hours, or 3 hours to 4 hours.

[0070] According to the present invention, the reaction ratio of the reactant and the amine compound may be an equivalent ratio of 1:1.1 to 3. Specifically, considering the yield of the NVP intermediate, the reaction ratio may be an equivalent ratio of 1:1.3 to 3, an equivalent ratio of 1:1.5 to 2.8, an equivalent ratio of 1:1.8 to 2.5, or an equivalent ratio of 1:1.9 to 2.2, but is not limited thereto.

[0071] The above amine compound may not be particularly limited as long as it is a compound capable of depolymerizing the polyhydroxyalkanoate included in the reactant. Specifically, the amine compound may include a compound selected from the group consisting of monoethanolamine, an aqueous monoethanolamine solution, ammonia, aqueous ammonia, urea, and urea water. When the amine compound includes the above compound, the conversion rate of the polyhydroxyalkanoate increases, thereby improving the yield of the NVP intermediate.

[0072] Meanwhile, according to the present invention, the intermediate included in the intermediate-containing product is not particularly limited, but may be N-(2-hydroxyethyl)-2-pyrrolidone. Since the intermediate is N-(2-hydroxyethyl)-2-pyrrolidone (HEP), the reaction steps for obtaining the NVP intermediate can be minimized, thereby increasing the efficiency of producing the NVP intermediate. Specifically, the N-(2-hydroxyethyl)-2-pyrrolidone can be the NVP intermediate, which is the target product in the present invention.

[0073] The above intermediate-containing product may include, in addition to the above intermediate, by-products such as γ-butyrolactone (GBL), 2-pyrrolidone, N-methylpyrrolidone (NMP), N-vinyl-2-pyrrolidone (NVP), 4-hydroxybutyric acid (4HB), and 4-hydroxy-N-(2-hydroxyethyl)butanamide (4HEBA).

[0074] In particular, the intermediate-containing product may contain a high content of the N-(2-hydroxyethyl)-2-pyrrolidone and a low content of the 4-hydroxy-N-(2-hydroxyethyl)butanamide. For example, the content of the N-(2-hydroxyethyl)-2-pyrrolidone contained in the intermediate-containing product may be, but is not limited to, 10 wt% to 99 wt%, 20 wt% to 90 wt%, 30 wt% to 80 wt%, 40 wt% to 70 wt%, or 50 wt% to 60 wt%, based on the total weight of the intermediate-containing product. In addition, the content of 4-hydroxy-N-(2-hydroxyethyl)butanamide included in the intermediate-containing product may be, but is not limited to, 0 wt% to 15 wt%, 0.2 wt% to 12 wt%, 0.6 wt% to 9 wt%, 1 wt% to 6 wt%, 1.4 wt% to 3 wt%, or 2 wt% to 2.5 wt% based on the total weight of the intermediate-containing product.

[0075]

[0076] According to the present invention, after producing an intermediate-containing product through steps (1) and (2), an NVP intermediate can be obtained through conventional filtering and extraction processes.

[0077] In this way, the present invention produces an N-vinyl-2-pyrrolidone intermediate through simple reaction steps of steps (1) and (2) without using an expensive metal catalyst, thereby achieving a high yield while reducing the cost consumed in producing the N-vinyl-2-pyrrolidone intermediate.

[0078] According to the present invention, the yield of the N-vinyl-2-pyrrolidone intermediate (e.g., N-(2-hydroxyethyl)-2-pyrrolidone) may be, but is not limited to, 35% or more, 38% or more, 40% or more, 43% or more, 45% or more, 50% or more, 53% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, or 85% or more (e.g., 35% to 95%, 40% to 93%, 50% to 90%, or 60% to 88%).

[0079]

[0080] N-vinyl-2-pyrrolidone intermediate

[0081] The N-vinyl-2-pyrrolidone intermediate (precursor) according to the present invention is manufactured by the above-described manufacturing method. This N-vinyl-2-pyrrolidone intermediate, manufactured by the above-described manufacturing method, exhibits high yield and high purity, and thus can be usefully used in the manufacture of N-vinyl-2-pyrrolidone, a high value-added chemical substance.

[0082]

[0083] N-vinyl-2-pyrrolidone and its preparation method

[0084] The N-vinyl-2-pyrrolidone according to the present invention is prepared from the above-described N-vinyl-2-pyrrolidone intermediate. Preparation of the N-vinyl-2-pyrrolidone using the above-described N-vinyl-2-pyrrolidone intermediate can be carried out using a commonly known preparation method.

[0085] For example, the method for producing N-vinyl-2-pyrrolidone may include, but is not limited to, a step of reacting an N-vinyl-2-pyrrolidone intermediate produced by the above-described production method with acetic anhydride to obtain an acetic acid ester intermediate; and a step of deacetating the obtained acetic acid ester intermediate. The reaction conditions for the reaction with acetic anhydride and the deacetation may be set in consideration of the yield of N-vinyl-2-pyrrolidone.

[0086] In addition, the method for producing N-vinyl-2-pyrrolidone may include, but is not limited to, a step of intramolecularly dehydrating the N-vinyl-2-pyrrolidone intermediate produced by the above-described method in the vapor phase in the presence of a catalyst. The reaction conditions for the dehydration may be set taking into account the yield of N-vinyl-2-pyrrolidone.

[0087] The present invention can produce the N-vinyl-2-pyrrolidone intermediate in a high yield, thereby increasing the production amount of the N-vinyl-2-pyrrolidone and, accordingly, lowering the unit price of the N-vinyl-2-pyrrolidone.

[0088] This N-vinyl-2-pyrrolidone can be usefully used as a synthetic raw material (monomer) for polyvinylpyrrolidone (PVP), which is widely used in the manufacture of cosmetics, foods, pharmaceuticals, paper, fibers, pigments, paints, electronic devices, etc.

[0089] The present invention is described in more detail through the following examples. However, the scope of the present invention is not limited to these examples.

[0090]

[0091] [Reagents, Test Equipment, and Analysis Equipment]

[0092] In the examples, comparative examples and test examples, isopropyl alcohol (Daejung Chemicals, HPLC grade), monoethanolamine (TCI, >99.0%), acetonitrile (BURDICK & JACKSON, HPLC grade), distilled water (MALLINCKRODT BAKER, HPLC grade), cationic polymer coagulant (FO4800VHM, SNF Korea), calcium carbonate (CaCO3) (Sigma Aldrich, >99%), ferric sulfate (Fe2(SO4)3) (Chemtech International Co., Ltd., iron content 10.5% or more), and sodium bicarbonate (NaHCO3) (Sigma Aldrich, >99%) were used as reagents.

[0093] As test equipment, a seal tube (CHEMGLASS LIFE SCIENCES, P05-132-128(1880-04)), a high-temperature and high-pressure reactor (Hanul Engineering Co., Ltd., Reactor system), a heating magnetic stirrer (Daehan Scientific Co., Ltd., DH.WMH03021), a press (Hwain Co., Ltd., Screw press dehydrator SP-30), and an electroosmosis dehydrator (Hwain Co., Ltd., EOD-500S) were used.

[0094] High-performance liquid chromatography (HPLC) and gas chromatography (GC) were used as analytical equipment. Specifically, the HPLC equipment used was the 1260 infinity equipment from Agilent Technologies, and the column used was the Capcell Pak C18 MG (4.6 mm × 250 mm × 5 μm, P / N 92635) from Osaka soda. At this time, the autosampler temperature was set to 15 °C, the column temperature was 35 °C, and the mobile phase solvent used was 3-distilled water containing 0.2% phosphoric acid and acetonitrile (ACN), and the analysis was performed at a mobile phase speed of 1 mL / min with a concentration gradient. The GC equipment used was a GC (Agilent Technologies, 8890) equipped with a DB-WAX (60 m × 250 μm × 0.25 μm) column. At this time, the inlet temperature was set to 250 ℃, and the flow rate was 1 mL / min. In addition, the FID (Flame ionization detector) detector temperature was set to 300 ℃ and then analyzed. Meanwhile, when analyzing the products, gas chromatography (GC) samples were diluted with isopropyl alcohol (IPA), and high-performance liquid chromatography (HPLC) samples were diluted with distilled water and analyzed.

[0095]

[0096] [Example 1]

[0097] Preparation of a reactant containing poly-4-hydroxybutyrate (P4HB)

[0098] A cationic polymer flocculating agent and distilled water were added to the fungal fermentation culture medium containing P4HB to flocculate. Subsequently, calcium carbonate (CaCO3), ferric sulfate (Fe2(SO4)3), and sodium bicarbonate (NaHCO3) were added to the flocculated fungal fermentation culture medium at a certain ratio to promote fluidity and chemical reaction. Next, the fungal flocculation was dehydrated using a press and an electroosmotic dehydrator to obtain a reactant containing P4HB. The content of P4HB contained in the obtained reactant was approximately 78.3 wt%, the total content of the added CaCO3, Fe2(SO4)3, and NaHCO3 was approximately 5 wt%, the moisture content was 0 wt%, and the remainder was cell debris.

[0099] Preparation of products containing N-(2-hydroxyethyl)-2-pyrrolidone (HEP)

[0100]

[0101] A batch-type high-temperature, high-pressure reactor was charged with 10 g of a reactant containing 78.3 wt% P4HB, 6.1 g of monoethanolamine (MEA), and 10 g of distilled water. Subsequently, the reactor was purged with N2 gas and a leak check was performed. The reaction was carried out at 1 bar and 250 °C for 3 hours while stirring at 500 rpm. After the temperature inside the reaction chamber reached 250 °C, the pressure (P2) during the reaction was confirmed to be 23 bar after about 30 minutes. After the reaction was completed and the temperature of the reaction chamber dropped to room temperature, the reaction solution was recovered. Subsequently, the recovered reaction solution was filtered through a syringe filter to remove biochar derived from the fungus, thereby obtaining a HEP-containing product.

[0102]

[0103] [Example 2]

[0104] Distilled water was added to the reactant containing P4HB used in Example 1 to prepare a reactant having a moisture content of 50 wt%, and a HEP-containing product was obtained through the same process as in Example 1.

[0105]

[0106] [Examples 3 to 10]

[0107] As shown in Table 1 below, a HEP-containing product was obtained through the same process as Example 1, except that the MEA equivalent was adjusted, the moisture content of the reactant was adjusted by adding distilled water as in Example 2, or the initial reaction pressure (P1) was adjusted by injecting N2 gas.

[0108]

[0109] [Example 1]

[0110] The HEP-containing products obtained in Examples 1 to 10 were analyzed by high-performance liquid chromatography (HPLC) and gas chromatography (GC), and the results are shown in Table 1 below.

[0111] Meanwhile, the relationship between HEP ​​yield, MEA equivalent, initial reaction pressure, and moisture content was summarized in a graph and shown in Fig. 2.

[0112]

[0113] Classification MEA Equivalent (eq) Moisture content (wt%) Initial reaction pressure (P1, bar) Reaction pressure (P2, bar) Reaction time (hr) Reaction temperature (℃) Yield (%) HEPGBL2-PyNMPNVP4HB4HEBA Example 11.1-123325054.61.55.40.60.04.03.2 Example 21.150125325040.72.78.30.90.12.27.9 Example 31.1503085325075.92.60.30.30.10.02.4 Example 41.15050109325081.21.40.30.30.00.01.7 Example 52.0-128325060.21.53.10.20.018.716.4Example 62.0-3079325057.81.90.20.20.00.00.0Example 72.050125325044.76.14.40.30.025.219.1Example 82.0503080325084.90.80.10.00.00.00.0Example 92.0753080325087.60.70.10.10.00.00.7Example 103.050123325050.72.93.10.10.011.09.9MEA: MonoethanolamineHEP: N-(2-hydroxyethyl)-2-pyrrolidoneNMP: N-MethylpyrrolidinoneNVP: N-Vinyl-2-pyrrolidone4HB: 4-Hydroxybutyric acidGBL: γ-butyrolactone4HEBA: 4-hydroxy-N-(2-hydroxyethyl)butanamide2-Py: 2-Pyrrolidone

[0114] Referring to Table 1 above, it can be confirmed that by producing a HEP-containing product at a reaction temperature exceeding 200°C as in the present invention, a HEP-containing product having a high HEP content, which is the intermediate desired in the present invention, is obtained.

[0115] Also, referring to FIG. 2, it can be confirmed that the HEP yield is improved by controlling the initial reaction pressure (P1) and moisture content (moisture content) as in the present invention. That is, although controlling the MEA equivalent did not have a significant effect on the change in the HEP yield, controlling the initial reaction pressure (P1) and moisture content had a significant effect on the change in the HEP yield. Specifically, looking at the evaluation results of the HEP yield according to the change in moisture content of the reactant including P4HB, when the initial reaction pressure (P1) was 30 bar, the HEP yield increased dramatically when the moisture content was 50 to 75 wt% compared to 0 wt% (see Examples 6, 8, and 9). In addition, as the initial reaction pressure (P1) or the pressure during the reaction (P2) increased, the HEP yield increased significantly.

[0116]

[0117] [Comparative Example 1]

[0118] A reactant containing P4HB was prepared through the same process as in Example 1.

[0119] Next, 0.2 g of the reactant with a P4HB content of 78.3 wt%, 0.122 g of monoethanolamine (MEA), and 0.2 g of distilled water were added to a 48 mL screw-cap sealed tube and stirred at 300 rpm to prepare a mixture. Subsequently, the prepared mixture was reacted using a heating stirrer at 1 bar and 120°C for 3 hours. After completion of the reaction, the reaction solution was recovered, and the product was obtained through a process of filtering the recovered reaction solution with a syringe filter to remove the biochar derived from the fungus.

[0120]

[0121] [Comparative Examples 2 to 5]

[0122] As shown in Table 2 below, a product was obtained through the same process as in Comparative Example 1, except that the MEA equivalent was adjusted or the moisture content of the reactant was adjusted by adding distilled water as in Example 2.

[0123]

[0124] [Example 2]

[0125] The products obtained in Comparative Examples 1 to 5 were analyzed by high-performance liquid chromatography (HPLC) and gas chromatography (GC), and the results are shown in Table 2 below.

[0126]

[0127] ClassificationMEAEquivalent(eq)Moisture content(wt%)Initial reaction pressure(bar)Reaction temperature(℃)Reaction time(h)Yield(%)HEP4HEBA4HBGBL2-PyComparative Example 11.1-112030.033.40.00.00.0Comparative Example 22-112030.068.02.00.00.0Comparative Example 3250112030.680.50.02.40.0Comparative Example 43-112030.291.21.90.00.0Comparative Example 5350112030.593.40.00.00.0MEA: MonoethanolamineHEP: N-(2-hydroxyethyl)-2-pyrrolidone4HB: 4-Hydroxybutyric acidGBL: γ-butyrolactone4HEBA: 4-hydroxy-N-(2-hydroxyethyl)butanamide2-Py: 2-Pyrrolidone

[0128] Referring to Table 2 above, it can be confirmed that when the product is manufactured at a reaction temperature of 120°C, which is a temperature that does not satisfy the conditions of the present invention, almost no conversion to HEP occurs, resulting in a product with a significantly low HEP content. In particular, when the MEA equivalent is 2 equivalents or more at a reaction temperature of 120°C, most of the P4HB is converted to 4HEBA rather than HEP, which is the intermediate desired in the present invention, and thus a significant amount of additional heat is required for conversion to HEP.

[0129]

[0130] [Comparative Examples 6 to 11]

[0131] A product was obtained through the same process as in Comparative Example 1, except that the MEA equivalent was adjusted while the reaction temperature was set to 200°C as shown in Table 3 below, or the moisture content of the reactant was adjusted by adding distilled water as in Example 2.

[0132]

[0133] [Example 3]

[0134] The products obtained in Comparative Examples 6 to 11 were analyzed by high-performance liquid chromatography (HPLC) and gas chromatography (GC), and the results are shown in Table 3 below.

[0135]

[0136] ClassificationMEAEquivalent(eq)Moisture content(wt%)Initial reaction pressure(bar)Reaction temperature(℃)Reaction time(h)Yield(%)HEP4HEBA4HBGBL2-PyComparative Example 61.1-120034.859.00.08.90.0Comparative Example 72-120037.480.14.30.00.0Comparative Example 82501200331.652.60.00.00.0Comparative Example 93-1200326.952.00.00.00.0Comparative Example 103751200329.363.20.00.00.0Comparative Example 11383120035.163.40.05.10.0MEA: MonoethanolamineHEP: N-(2-hydroxyethyl)-2-pyrrolidone4HB: 4-Hydroxybutyric acidGBL: γ-butyrolactone4HEBA: 4-hydroxy-N-(2-hydroxyethyl)butanamide2-Py: 2-Pyrrolidone

[0137] Referring to Table 3 above, it can be confirmed that even when the reaction temperature is raised to 200°C, the amount of heat required to convert P4HB into HEP is insufficient, resulting in a product with a low HEP content. In addition, when the moisture content of the reactant containing P4HB exceeds 50 wt%, the yield of 4HEBA and other by-products, but not HEP, tends to increase.

Claims

1. (1) A step of preparing a reactant containing polyhydroxyalkanoate obtained through microbial culture; and (2) A method for producing an N-vinyl-2-pyrrolidone intermediate, comprising a step of reacting a reactant containing the polyhydroxyalkanoate and an amine compound at a temperature exceeding 200° C. to produce a product containing an intermediate.

2. In paragraph 1, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the polyhydroxyalkanoate in the above step (1) contains a repeating unit derived from 4-hydroxybutyrate.

3. In paragraph 1, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the content of the polyhydroxyalkanoate included in the reactant in the step (1) is 60 wt% to 90 wt% based on the total weight of the reactant.

4. In paragraph 1, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the moisture content of the reactant in the above step (1) is 0 wt% to 80 wt% based on the total weight of the reactant.

5. In paragraph 1, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the reactant in the above step (1) further comprises an inorganic substance.

6. In paragraph 5, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the inorganic content is greater than 0 wt% to 10 wt% based on the total weight of the reactants.

7. In paragraph 5, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the above-mentioned inorganic material comprises at least one selected from the group consisting of calcium carbonate (CaCO3), ferric sulfate (Fe2(SO4)3), and sodium bicarbonate (NaHCO3).

8. In paragraph 1, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the initial reaction pressure of the reactant and the amine compound in the above step (2) is 1 bar to 120 bar.

9. In paragraph 1, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein in the step (2), the amine compound comprises a compound selected from the group consisting of monoethanolamine, an aqueous monoethanolamine solution, ammonia, aqueous ammonia, urea, and urea water.

10. In paragraph 1, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the reactant and the amine compound react in an equivalent ratio of 1:1.1 to 3 in the above step (2).

11. In paragraph 1, A method for producing an N-vinyl-2-pyrrolidone intermediate, wherein the intermediate in the above step (2) is N-(2-hydroxyethyl)-2-pyrrolidone.

12. N-vinyl-2-pyrrolidone intermediate manufactured by the manufacturing method of paragraph 1.

13. N-vinyl-2-pyrrolidone, prepared from the N-vinyl-2-pyrrolidone intermediate of claim 12.

14. A step of reacting the N-vinyl-2-pyrrolidone intermediate manufactured by the manufacturing method of Article 1 with acetic anhydride to obtain an acetic acid ester intermediate; and A method for producing N-vinyl-2-pyrrolidone, comprising a step of deacetating the obtained acetic acid ester intermediate.

15. A method for producing N-vinyl-2-pyrrolidone, comprising a step of intramolecularly dehydrating an N-vinyl-2-pyrrolidone intermediate produced by the method of claim 1 in the gas phase in the presence of a catalyst.

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