Organic acid prepolymer composition, organic acid polymer, and method for preparing same

Abstract

The present invention relates to: a method for preparing an organic acid prepolymer and an organic acid polymer by polymerizing and washing a low-purity organic acid composition comprising an inorganic compound; the organic acid prepolymer composition; and the organic acid polymer.

Description

Organic acid prepolymer composition, organic acid polymer and method for producing the same

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0010984, filed January 24, 2024, Korean Patent Application No. 10-2024-0134813, filed October 4, 2024, Korean Patent Application No. 10-2024-0157262, filed November 7, 2024, Korean Patent Application No. 10-2024-0175138, filed November 29, 2024, Korean Patent Application No. 10-2025-0001746, filed January 6, 2025, and Korean Patent Application No. 10-2025-0010162, filed January 23, 2025, the entire contents of which are hereby incorporated by reference herein. Included as part of.

[0003] The present invention relates to a high-purity organic acid prepolymer composition, an organic acid polymer, and a method for producing the same.

[0004] Organic acids are commercially important chemicals with diverse applications in the food, cosmetics, pharmaceutical, and polymer industries. Representative organic acids include lactic acid and 3-hydroxypropionic acid (3-HP). Among them, 3-hydroxypropionic acid (3HP) is a valuable raw material for the production of acrylic acid, 1,3-propanediol, acrylamide, malonic acid, and biopolymers.

[0005] Organic acids are produced largely through two methods: chemical and biological. However, chemical methods are criticized as being unfriendly due to the high cost of initial materials and the generation of toxic substances during the production process. Therefore, environmentally friendly bioprocesses are gaining attention.

[0006] When producing organic acids through microbial fermentation, byproducts other than organic acids such as 3-hydroxypropionic acid are also produced during the fermentation process. Therefore, purification processes such as electrodialysis and ion exchange resins are required to extract and separate the organic acids from the fermentation broth. These purification processes are lengthy and expensive. Therefore, there is a need for a method to efficiently convert raw materials such as biopolymers into low-purity organic acids containing byproducts.

[0007] The present invention relates to a method for producing high purity and high molecular weight oligomers, prepolymers and polymers from low purity organic acid compositions containing inorganic compounds efficiently and at low process cost.

[0008] In the present specification, a method for producing an organic acid prepolymer is provided, comprising the steps of polymerizing an organic acid composition containing an inorganic compound to produce an oligomer and / or a prepolymer; and the step of washing the oligomer and / or prepolymer with a washing solution.

[0009] In addition, the present specification provides a method for producing an organic acid polymer, comprising the steps of: polymerizing an organic acid composition containing an inorganic compound to produce an oligomer and / or a prepolymer; washing the oligomer and / or prepolymer with a washing solution; and polymerizing the washed oligomer and / or prepolymer to produce a polymer.

[0010] In addition, the present specification provides an organic acid prepolymer composition comprising an organic acid composition containing an inorganic compound, wherein the organic acid prepolymer composition comprises a polymerized organic acid prepolymer, and the inorganic compound is removed by washing.

[0011] In addition, in the present specification, an organic acid polymer polymerized with the organic acid prepolymer composition is provided.

[0012] Hereinafter, the organic acid prepolymer composition, organic acid polymer, and method for producing the same according to specific embodiments of the invention will be described in more detail.

[0013] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0014] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

[0015] Furthermore, unless the steps constituting the manufacturing method described herein are explicitly stated to be sequential or consecutive, or there is another special order, the order of one step constituting a manufacturing method from another step is not limited to the order described in the specification. Accordingly, the order of the steps constituting the manufacturing method may be varied within a range readily understandable to those skilled in the art, and in such cases, any subsequent changes apparent to those skilled in the art are within the scope of the present invention.

[0016] In this specification, organic acid means an organic compound having acidity, and may be, for example, an organic compound containing a carboxyl group or a sulfonic group.

[0017] In this specification, alkali metal may mean both alkali metal and alkaline earth metal.

[0018]

[0019] According to one embodiment of the invention, a method for producing an organic acid prepolymer is provided, comprising: a step of polymerizing an organic acid composition containing an inorganic compound to produce an oligomer and / or a prepolymer; and a step of washing the oligomer and / or prepolymer with a washing solution.

[0020] In the past, in order to manufacture high value-added organic acid oligomers, prepolymers and polymers with biodegradability, a process was used to manufacture an organic acid fermentation liquid through microbial fermentation and purify it to recover a high-purity organic acid as a reaction raw material. However, in order to recover a high-purity organic acid, a purification process of the fermentation liquid, such as an electrodialysis or ion exchange resin process, was additionally performed, which resulted in a complex process and high process operation costs.

[0021] Accordingly, the inventors of the present invention studied a process for producing high-purity organic acid oligomers, prepolymers, and polymers without purifying the microbial fermentation solution through a complicated or expensive purification process such as electrodialysis or an ion exchange resin process, and confirmed that when an organic acid composition containing an inorganic compound is polymerized to produce an oligomer and / or prepolymer and then the oligomer and / or prepolymer is washed, it is possible to produce organic acid oligomers, prepolymers, and polymers having high purity and biodegradability, similar to a conventional process for polymerizing high-purity organic acids, while also producing a polymer having a high molecular weight, thereby completing the invention.

[0022] The above-described inorganic compound-containing organic acid composition can be recovered from a fermented liquid fermented by a strain having organic acid production ability. However, since the above-described inorganic compound-containing organic acid composition does not undergo an additional inorganic purification process, it may contain a large amount of inorganic impurities such as inorganic compounds. For example, the purity of the organic acid in the inorganic compound-containing organic acid composition may be 90% or less, 88% or less, 85% or less, 83% or less, 80% or less, 75% or less, 70% or less, 65% or less, 50% or less, or 5% or more and 40% or less.

[0023] The organic acid is not particularly limited as long as it can be produced through microbial fermentation, but may be, for example, one or more selected from the group consisting of lactic acid, 3-hydroxypropionic acid, butyric acid, acetic acid, propionic acid, succinic acid, and salts thereof, and may be lactic acid or 3-hydroxypropionic acid for producing high value-added oligomers, prepolymers, polymers, etc.

[0024]

[0025] The method for producing an organic acid prepolymer according to the above embodiment may further include a step of producing an organic acid fermentation liquid by fermenting a strain having an organic acid production ability before the step of producing an oligomer and / or prepolymer by polymerizing the organic acid composition containing the inorganic compound.

[0026] Microorganisms, such as strains capable of producing organic acids, can produce an organic acid fermentation solution by fermenting low-molecular-weight sugars. These microorganisms can be natural or engineered microorganisms, and the microorganisms can be, for example, bacteria, such as cellulolytic bacteria, fungi, such as yeast, plants, or protists, such as algae, protozoa, or fungal-like protists, such as slime molds. If the organisms do not cause an adverse reaction, a mixture of organisms can be used.

[0027] For example, a strain having 3-hydroxypropionic acid production ability may include a gene encoding one or more proteins selected from the group consisting of glycerol dehydratase and aldehyde dehydrogenase, or two of the above. In one example, the 3-hydroxypropionic acid producing strain may further include a gene (gdrAB) encoding glycerol dehydratase reactivase (GdrAB). In one example, the 3-hydroxypropionic acid producing strain may further include a gene encoding vitamin B. 12 It may be a strain capable of biosynthesizing .

[0028] The above glycerol dehydratase may be encoded by, but is not limited to, the dhaB (GenBank accession no. U30903.1) gene. The dhaB gene may be an enzyme derived from, but is not limited to, Klebsiella pneumonia. The gene encoding the glycerol dehydratase may include a gene encoding dhaB1, dhaB2, and / or dhaB3. The glycerol dehydratase protein and the gene encoding the same may include mutations in the gene and / or amino acid sequence within a range that maintains an enzymatic activity that decomposes glycerol into 3-hydroxypropanal (3-HPA) and water (H2O).

[0029] The gene (aldH) encoding the above aldehyde dehydrogenase (ALDH) may be, for example, an aldH (GenBank Accession no. U00096.3; EaldH) gene derived from Escherichia coli or an E. coli K12 MG1655 cell line, a puuC gene derived from Klebsiella pneumoniae, and / or a KGSADH gene derived from Azospirillum brasilense, but is not limited thereto. The above aldehyde dehydrogenase protein and the gene encoding the same may include mutations in the gene and / or amino acid sequence within a range that maintains the activity for producing 3-hydroxypropionic acid from 3-hydroxypropanal.

[0030] The medium for producing the above fermentation solution may be selected without limitation within the scope of the purpose for producing organic acids. In one example, the medium may include glycerol as a carbon source. In another example, the medium may be, but is not limited to, waste glycerol (crude glycerol) and / or pretreated waste glycerol. In one example, the production medium may include vitamin B. 12 may additionally include:

[0031] In the step of producing an organic acid fermentation liquid by fermenting a strain having the above organic acid production ability, the concentration of the organic acid contained in the organic acid fermentation liquid may be 1 g / L or more and 200 g / L or less, 10 g / L or more and 150 g / L or less, 30 g / L or more and 130 g / L or less, or 40 g / L or more and 100 g / L or less.

[0032] In addition, the fermentation may be a neutral fermentation, for example, the pH may be maintained in a range of 6.0 to 8.0, 6.5 to 7.5, or 6.5 to 7.5, but is not limited thereto. The pH range may be appropriately adjusted as needed. The alkali metal salt may be added for the neutral fermentation. The alkali metal salt may be Mg 2+ , Ca 2+ Or it may include a mixture thereof. In addition, the alkali metal salt may be, but is not limited to, Ca(OH)2 or Mg(OH)2.

[0033]

[0034] The method for producing an organic acid prepolymer according to the above embodiment may further include, after the step of producing the organic acid fermentation liquid, a step of mixing the fermentation liquid and an organic solvent to precipitate organic acid salt crystals.

[0035] In order to recover organic acid salt crystals from the fermentation broth, an organic solvent may be added dropwise to the fermentation broth, or after adding the fermentation broth to the organic solvent, the fermentation broth and the organic solvent may be mixed, and the organic acid salt may be precipitated by inducing granulation of the organic acid salt crystals. The precipitation may be performed at a temperature of -10°C to 40°C, -9°C to 35°C, -8°C to 30°C, -7°C to 30°C, -6°C to 25°C, -5°C to 20°C, or 0°C to 15°C.

[0036] The organic solvent may be, but is not limited to, alcohol, water, ether, ketone, halogenated hydrocarbon, aromatic hydrocarbon, etc.

[0037] The alcohol may be, for example, one or more selected from the group consisting of straight-chain or branched alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, and propanol (e.g., isopropyl alcohol).

[0038] The ether may be ethyl ether, dioxane, tetrahydrobutane, etc., the ketone may be acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, etc., the halogenated hydrocarbon may be dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, etc., and the aromatic hydrocarbon may be benzene, toluene, xylene, etc.

[0039] Additionally, the organic solvent may have a concentration of 10 to 100% (v / v), 20 to 100 (v / v), 30 to 100 (v / v), 40 to 100 (v / v), 50 to 100 (v / v), 60 to 100 (v / v), 70 to 100 (v / v), 80 to 100 (v / v), 90 to 100 (v / v), 95 to 100 (v / v), or 98 to 100 (v / v), for example, 99% (v / v).

[0040] The amount of the organic solvent added may be 5 to 10 times, 6 to 9 times, or 7 to 8 times that of the fermentation liquid.

[0041]

[0042] The method for producing an organic acid prepolymer according to the above embodiment may further include, after the step of mixing the fermentation solution and the organic solvent to precipitate organic acid salt crystals, the step of preparing a solution dissolving the organic acid salt crystals and adding an acid to control the pH to 5 or lower.

[0043] For example, after precipitating the organic acid salt crystals, the organic acid salt crystals can be filtered, a solution dissolving the filtered organic acid salt crystals can be prepared, and an acid can be added to control the pH to 5 or lower.

[0044] In addition, the step of introducing the acid may protonate the organic acid by titrating the acid to produce a salt. At this time, the acid is not particularly limited as long as it can control the pH of the fermentation solution to 5 or lower, and may be, for example, one selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, carbonic acid, and nitric acid. In addition, the salt produced by acid titration may be CaSO4(s) or MgSO4(s), but is not limited thereto. In addition, by introducing the acid into the fermentation solution, the pH of the fermentation solution may be controlled to 5.0 or lower, 4.0 or lower, 3.0 or lower, 2.0 or lower, 1.0 or lower, or 0.5 or lower.

[0045]

[0046] The above method for producing an organic acid prepolymer includes a step of polymerizing an organic acid composition containing an inorganic compound to produce an oligomer and / or a prepolymer, and the organic acid composition containing an inorganic compound may include inorganic impurities such as inorganic compounds depending on a metal salt used during fermentation, and is not limited thereto, but for example, the organic acid composition containing an inorganic compound may include magnesium, calcium, sodium, phosphorus, sulfur, potassium, chlorine, salts thereof, derivatives thereof, or mixtures thereof.

[0047] In addition, the organic acid composition containing the inorganic compound may include one or more elements selected from the group consisting of magnesium element, calcium element, sodium element, phosphorus element, sulfur element, potassium element, and chlorine element, and the content of the element based on 100 wt% of the organic acid composition containing the inorganic compound may be 5.0 wt% or less, for example, 3.0 wt% or less, 2.0 wt% or less, or 1.0 wt% or less.

[0048] For example, the organic acid composition containing the inorganic compound may have a concentration of calcium element (Ca) of 50 ppm or more, 100 ppm or more, 200 ppm or more, 300 ppm or more, and 3,000 ppm or less.

[0049] In addition, the organic acid composition containing the inorganic compound may have a concentration of sodium element (Na) of 300 ppm or more, 500 ppm or more, 700 ppm or more, 1,000 ppm or more, 1,300 ppm or more, 1,500 ppm or more, 1,800 ppm or more and 3,000 ppm or less.

[0050] In addition, the organic acid composition containing the inorganic compound may have a concentration of elemental phosphorus (P) of 1 ppm or more, 5 ppm or more, 8 ppm or more, 10 ppm or more and 3,000 ppm or less.

[0051] In addition, the organic acid composition containing the inorganic compound may have a concentration of elemental sulfur (S) of 300 ppm or more, 500 ppm or more, 700 ppm or more, 1,000 ppm or more, 1,300 ppm or more, 1,500 ppm or more, 1,800 ppm or more and 3,000 ppm or less.

[0052] In addition, the organic acid composition containing the inorganic compound may have a concentration of potassium element (K) of 50 ppm or more, 100 ppm or more, 200 ppm or more, 300 ppm or more and 3,000 ppm or less.

[0053] In addition, the organic acid composition containing the inorganic compound may have a concentration of chlorine element (Cl) of 300 ppm or more, 500 ppm or more, 700 ppm or more, 1,000 ppm or more, 1,500 ppm or more, 2,000 ppm or more, 2,500 ppm or more, 3,500 ppm or more and 10,000 ppm or less.

[0054] Meanwhile, the concentration of the above elements can be measured using ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometry).

[0055]

[0056] In the step of polymerizing the organic acid composition containing the inorganic compound to produce an oligomer and / or a prepolymer, the polymerization may be performed at a temperature of 75°C or more and 200°C or less, for example, 80°C or more, 85°C or more, 90°C or more, 120°C or more, 150°C or more, 200°C or more, 180°C or less, 160°C or less, 150°C or less, 130°C or less, 125°C or less, 120°C or less, 115°C or less, or 110°C or less. If the polymerization temperature is too low, the molecular weight of the oligomer and / or prepolymer may be low, and if the polymerization temperature is too high, polymerization of the organic acid may be difficult to proceed.

[0057] In addition, the polymerization of the organic acid composition containing the inorganic compound can be performed at a pressure of 1 torr or more and 760 torr or less for 1 hour or more and 10 hours or less, for example, at a pressure of 1 torr or more, 5 torr or more, 7 torr or more, 10 torr or more, 50 torr or more, 100 torr or more, 200 torr or more, or 300 torr or more, and 700 torr or less, 500 torr or less, 300 torr or less, 200 torr or less, 150 torr or less, 100 torr or less, 70 torr or less, or 50 torr or less. In addition, the reaction time for polymerization of the organic acid composition containing the inorganic compound may be appropriately considered in consideration of the molecular weight, yield, etc. of the oligomer and prepolymer produced, and is preferably performed for 1 to 10 hours, 2 to 8 hours, or 3 to 5 hours.

[0058] In addition, the polymerization of the organic acid composition containing the inorganic compound may be carried out in the absence of a catalyst, or in the presence of a tin-based catalyst and / or a sulfonic acid-based catalyst. The tin-based catalyst may be dibutyl tin dilaureate (DBTDL), dioctyl tin dilaurate (DOTDL), dibutyl tin diacetate, stannous acetate, or tin caprylate, and the sulfonic acid-based catalyst may be, for example, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid. The catalyst may be used in an amount of 0.05 mol% to 0.5 mol%, 0.1 mol% to 0.4 mol%, or 0.2 mol% to 0.4 mol% relative to the organic acid.

[0059] The oligomer and prepolymer manufactured by the above polymerization may have a weight average molecular weight of 800 or more, 1,000 or more, 1,300 or more, 1,500 or more, 2,000 or more, 2,500 or more, or 3,000 or more, and 15,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, or 7,000 or less.

[0060] Additionally, the oligomer and prepolymer may have a number average molecular weight of 700 or more, 800 or more, 900 or more, 1,000 or more, 1,200 or more, 1,500 or more, or 2,000 or more, and 15,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, or 7,000 or less.

[0061]

[0062] The method for producing an organic acid prepolymer according to the above embodiment may include a step of washing the oligomer and / or prepolymer with a washing solution.

[0063] The above-mentioned cleaning solution may be water, distilled water, or a solution containing a basic compound, such as ammonia water. In addition, the basic compound is not particularly limited as long as it is a basic compound that does not contain a metal ion, but examples thereof include quaternary ammonium compounds, amines, etc.

[0064] Examples of the above quaternary ammonium compounds include tetramethylammonium hydroxide (TMAH), trimethyl-2-hydroxyethylammonium hydroxide (choline), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenyl ammonium hydroxide, and benzyltrimethyl ammonium hydroxide.

[0065] The above amine may be a first-grade aliphatic amine, a second-grade aliphatic amine, a tertiary aliphatic amine, or an alicyclic amine. For example, the first-grade aliphatic amine may be monoethanol amine, ethylene diamine, 2-(2-amino ethoxy ethanol), 2-(2-amino ethylamino) ethanol, diethylene triamine, triethylene tetramine, etc.; the second-grade aliphatic amine may be diethanol amine, N-methyl amino ethanol, N-hydroxy ethyl amino ethanol, dipropyl amine, 2-ethyl amino ethanol, etc.; the tertiary aliphatic amine may be triethanol amine, dimethyl amino ethanol, ethyldiethanol amine, etc.; and the alicyclic amine may be cyclopentyl amine, cyclohexyl amine, etc.

[0066] The content of the basic compound included in the above-mentioned cleaning solution may be included in an amount of 1 wt% or more, 3 wt% or more, 5 wt% or more, 7 wt% or more, 8 wt% or more, or 10 wt% or more, and may be included in an amount of 30 wt% or less, 25 wt% or less, 20 wt% or less, 15 wt% or less, or 10 wt% or less, based on 100 wt% of the total cleaning solution.

[0067]

[0068] When washing the above oligomer and / or prepolymer with a washing solution, the washing temperature may be 50°C or higher and 95°C or lower, for example, washing may be performed at a temperature of 55°C or higher, 60°C or higher, or 70°C or higher, and washing may be performed at a temperature of 93°C or lower, 90°C or lower, 85°C or lower, 80°C or lower, or 75°C or lower.

[0069] If the above washing temperature is too low, the prepolymer may not dissolve, making washing difficult, and if the washing temperature is too high, the oligomer and / or prepolymer may be thermally decomposed.

[0070] When washing the above oligomer and / or prepolymer with a washing solution, the washing solution can be used in an amount of 0.5 times or more and 30 times or less by weight relative to the weight of the oligomer and / or prepolymer, for example, 0.7 times or more, 1.0 times or more, 2.0 times or more, 3.0 times or more, 4.0 times or more by weight, and 28 times or less, 25 times or less, 23 times or less, or 20 times or less by weight.

[0071] Additionally, the purity of the oligomer and / or prepolymer washed by the washing process may be 90% or more, 93% or more, 95% or more, 98% or more, 99% or more, or 100%.

[0072]

[0073] The method for manufacturing an organic acid prepolymer according to the above embodiment may further include, after the step of washing the oligomer and / or prepolymer with a washing solution, a step of separating the washed oligomer and / or prepolymer into a solid or liquid solution.

[0074] The above solid-liquid separation process can be performed through filtration, etc., and the washed oligomer and / or prepolymer and the washing liquid can be separated using a filtration flask and a vacuum pump, etc.

[0075] In addition, since the oligomer and / or prepolymer in a molten state has hydrophobicity or reduced hydrophilicity, unlike the hydrophilic washing liquid, and can be separated from the washing liquid, the oligomer and / or prepolymer can be recovered by separating the supernatant and the lower layer through centrifugation in the liquid-liquid separation process.

[0076] Additionally, the cleaning solution recovered through the separation process can be reused in additional cleaning processes.

[0077]

[0078] According to another embodiment of the invention, an organic acid prepolymer composition containing an inorganic compound is provided, wherein the organic acid prepolymer composition comprises a polymerized organic acid prepolymer, and the inorganic compound is removed by washing.

[0079] At this time, the organic acid prepolymer may be a 3-hydroxypropionic acid prepolymer. In addition, the organic acid prepolymer composition may be manufactured by the organic acid prepolymer manufacturing method according to the above embodiment.

[0080] Meanwhile, the above prepolymer may mean an oligomer.

[0081]

[0082] In addition, the organic acid composition containing the inorganic compound is as described above in the method for producing an organic acid prepolymer according to the above embodiment, and may be, for example, recovered from a fermentation broth obtained by fermenting a strain having organic acid production ability. The fermentation broth may contain a large amount of inorganic impurities such as inorganic compounds, and the organic acid prepolymer composition may have a high purity as the inorganic compounds are removed by washing. In addition, in addition to the byproducts of the fermentation broth, the catalyst used in the polymerization may be removed by washing, and thus may exhibit a high purity. For example, the purity of the organic acid prepolymer may be 90% or more, 93% or more, 95% or more, 98% or more, 99% or more, or 100%.

[0083] For example, the washed organic acid prepolymer may have a concentration of elemental calcium (Ca) of 200 ppm or less, 150 ppm or less, 100 ppm or less, 50 ppm or less, 30 ppm or less, 15 ppm or less, or 1 ppm or more and 10 ppm or less.

[0084] Additionally, the washed organic acid prepolymer may have a concentration of elemental sodium (Na) of 1,000 ppm or less, 500 ppm or less, 100 ppm or less, 50 ppm or less, 20 ppm or less, or 1 ppm or more and 15 ppm or less.

[0085] Additionally, the washed organic acid prepolymer may have a concentration of elemental phosphorus (P) of 50 ppm or less, 30 ppm or less, 15 ppm or less, or 1 ppm or more and 10 ppm or less.

[0086] Additionally, the washed organic acid prepolymer may have a concentration of elemental sulfur (S) of 1,000 ppm or less, 500 ppm or less, 300 ppm or less, 200 ppm or less, 100 ppm or less, or 1 ppm or more and 80 ppm or less.

[0087] Additionally, the washed organic acid prepolymer may have a concentration of potassium element (K) of 200 ppm or less, 100 ppm or less, 50 ppm or less, 30 ppm or less, 15 ppm or less, or 1 ppm or more and 10 ppm or less.

[0088] Additionally, the washed organic acid prepolymer may have a concentration of chlorine element (Cl) of 1,000 ppm or less, 500 ppm or less, 100 ppm or less, 50 ppm or less, 20 ppm or less, 15 ppm or less, or 1 ppm or more and 10 ppm or less.

[0089] Meanwhile, the concentration of the above elements can be measured using ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometry).

[0090]

[0091] In addition, the washing is as described above in the method for producing an organic acid prepolymer according to the above embodiment.

[0092] The above prepolymer may have a weight average molecular weight of 800 or more, 1,000 or more, 1,300 or more, 1,500 or more, 2,000 or more, 2,500 or more, or 3,000 or more, and 15,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, or 7,000 or less, and a number average molecular weight of 700 or more, 800 or more, 900 or more, 1,000 or more, 1,200 or more, 1,500 or more, or 2,000 or more, and 15,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, or 7,000 or less.

[0093]

[0094] According to another embodiment of the invention, a method for producing an organic acid polymer is provided, further comprising the steps of: polymerizing an organic acid composition containing an inorganic compound to produce an oligomer and / or a prepolymer; washing the oligomer and / or prepolymer with a washing solution; and polymerizing the washed oligomer and / or prepolymer to produce a polymer.

[0095] The step of polymerizing the organic acid composition containing the above inorganic compound to produce an oligomer and / or prepolymer and the step of washing the oligomer and / or prepolymer with a washing solution are as described above in the method for producing an organic acid prepolymer according to the above embodiment.

[0096] In the step of manufacturing a polymer by polymerizing the above-mentioned washed oligomer and / or prepolymer, the polymerization may be performed at a temperature of 90°C or more and 200°C or less and a pressure of 0.01 torr or more and 760 torr or less for 20 hours or more and 100 hours or less. For example, the reaction temperature of the polymerization may be 95°C or more and 180°C or less, 100°C or more and 150°C or less, or 105°C or more and 115°C or less. In addition, the pressure of the polymerization may be 700 torr or less, 500 torr or less, 300 torr or less, 200 torr or less, 100 torr or less, 50 torr or less, 40 torr or less, or 30 torr or less, and 0.01 torr or more, 0.02 torr or more, 0.03 torr or more, 0.04 torr or more, 0.05 torr or more, 0.06 torr or more, 0.07 torr or more, 0.08 torr or more, 0.09 torr or more, or 0.10 torr or more. The reaction time of the polymerization may be appropriately considered in consideration of the molecular weight, yield, etc. of the polymer produced, and is preferably performed for 20 to 90 hours, 40 to 80 hours, or 50 to 70 hours.

[0097] Additionally, the polymerization may be carried out in the presence of a tin-based catalyst and / or a sulfonic acid-based catalyst. The tin-based catalyst may be dibutyl tin dilaureate (DBTDL), dioctyl tin dilaurate (DOTDL), dibutyl tin diacetate, stannous acetate, or tin caprylate, and the sulfonic acid-based catalyst may be, for example, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid. The catalyst may be used in an amount of 0.05 mol% to 0.5 mol%, 0.1 mol% to 0.4 mol%, or 0.2 mol% to 0.4 mol% relative to the organic acid and / or prepolymer.

[0098]

[0099] According to another embodiment of the invention, the organic acid prepolymer composition provides a polymerized organic acid polymer.

[0100] The above organic acid polymer may be a 3-hydroxypropionic acid polymer.

[0101] Additionally, the organic acid prepolymer composition may be manufactured by the organic acid prepolymer manufacturing method according to the above embodiment.

[0102] The above organic acid polymer may have a weight average molecular weight of 10,000 or more, 11,000 or more, 15,000 or more, 17,000 or more, 20,000 or more, 21,000 or more, 40,000 or less, 39,000 or less, 38,000 or less, 37,000 or less, 36,000 or less, or 35,000 or less.

[0103] Additionally, the organic acid polymer may have a number average molecular weight of 7,000 or more, for example, 7,100 or more, 7,200 or more, 7,300 or more, 7,400 or more, 8,000 or more, 8,500 or more, 9,000 or more, 9,500 or more, and 23,000 or less, 22,000 or less, 21,000 or less, 20,000 or less, or 19,000 or less.

[0104] According to the present invention, a method for producing high purity and high molecular weight oligomers, prepolymers and polymers using a low purity organic acid composition containing an inorganic compound can be provided at an efficient and low process cost.

[0105] Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the present invention, and the content of the present invention is not limited by the following examples.

[0106]

[0107] Preparation Example 1. Production of 3-hydroxypropionic acid

[0108] A recombinant vector was constructed by introducing genes encoding glycerol dehydratase and aldehyde dehydrogenase, which are known to produce 3-hydroxypropionic acid (3HP) using glycerol as a substrate. The constructed recombinant vector was introduced into E. coli W3110 strain to construct a 3-hydroxypropionic acid-producing strain.

[0109] More specifically, the BtuR gene encoding adenosyltransferase was cloned into plasmid pCDF containing a gene encoding glycerol dehydratase (dhaB), a gene encoding aldehyde dehydrogenase (aldH), and a gene encoding glycerol dehydratase reactivase (gdrAB), and the pCDF_J23101_dhaB_gdrAB_J23100_aldH_btuR vector was introduced into W3110 strain (KCCM 40219) by electroporation using an electroporation device (Bio-Rad, Gene Pulser Xcell) to construct a 3-hydroxypropionic acid producing strain. The process for producing a 3-hydroxypropionic acid producing strain of Preparation Example 1 and the vector, primers, and enzymes used were performed with reference to Example 1 of Korean Patent Publication No. 10-2020-0051375.

[0110] The prepared 3-hydroxypropionic acid-producing strain was fermented at 35°C in a 5 L fermenter using crude glycerol as a carbon source to produce 3-hydroxypropionic acid. To prevent a decrease in pH due to 3-hydroxypropionic acid production, calcium hydroxide (Ca(OH)2), an alkali metal salt, was added to maintain the pH at neutral during fermentation.

[0111] After fermentation culture, cells were removed by centrifugation, and organic impurities were purified to prepare a 3-hydroxypropionic acid solution (concentration 5-30 g / L).

[0112]

[0113] Example 1

[0114] (1) Prepolymer manufacturing

[0115] 500 g (content 11.7%) of the 3-hydroxypropionic acid solution prepared in Preparation Example 1 was added to a 1000 ml glass reactor, and vacuum distillation was performed at a temperature of 40 to 50°C to prepare a concentrated 3-hydroxypropionic acid aqueous solution (content 72%). When solids precipitated during concentration, they were further removed by filtration. 80 g of the 3-hydroxypropionic acid aqueous solution and 0.5 g of a p-toluenesulfonic acid (p-TSA) catalyst were added to an oil bath, and polymerization was performed at 90°C and 70 torr pressure for 2 hours to prepare a 3-hydroxypropionic acid prepolymer.

[0116] (2) Prepolymer washing

[0117] The 3-hydroxypropionic acid prepolymer was washed with a washing solution at 85°C using water. The washing solution was used in an amount three times the weight of the 3-hydroxypropionic acid prepolymer. Afterwards, the washed prepolymer and the washing solution were separated into solid and liquid using a filter flask and a vacuum pump, and the washed prepolymer was recovered. The prepolymer was dried in an oven at 40°C for 20 hours, and the dried prepolymer was finally recovered.

[0118] (3) Polymer manufacturing

[0119] 30 g of the above prepolymer and 0.25 g of p-toluenesulfonic acid (p-TSA) catalyst were added to an oil bath, and polymerization was performed at 95°C and 1 torr pressure for 72 hours to produce a polymer, i.e., poly(3-hydroxypropionate).

[0120]

[0121] Example 2

[0122] (1) Prepolymer manufacturing

[0123] 500 g (content 11.7%) of the 3-hydroxypropionic acid solution prepared in Preparation Example 1 was added to a 1000 ml glass reactor, and vacuum distillation was performed at a temperature of 40 to 50° C. to prepare a concentrated 3-hydroxypropionic acid aqueous solution (content 72%). 80 g of the 3-hydroxypropionic acid aqueous solution and 0.5 g of a p-toluenesulfonic acid (p-TSA) catalyst were added to an oil bath, and polymerization was performed at a temperature of 90° C. and a pressure of 70 torr for 2 hours to prepare a 3-hydroxypropionic acid prepolymer.

[0124] (2) Prepolymer washing

[0125] A washing solution was prepared by mixing 500 ml of water and 5 ml of ammonia water, and the 3-hydroxypropionic acid prepolymer was washed with the washing solution at a temperature of 85°C. The washing solution was used in an amount 1 times the weight of the 3-hydroxypropionic acid prepolymer. Thereafter, the washed prepolymer and the washing solution were separated into liquid and liquid using a filter flask and a vacuum pump, and the washed prepolymer was recovered.

[0126] (3) Polymer manufacturing

[0127] 30 g of the above prepolymer and 0.25 g of p-toluenesulfonic acid (p-TSA) catalyst were added to an oil bath, and polymerization was performed at a temperature of 90°C and a pressure of 1 torr for 30 hours to produce a polymer, i.e., poly(3-hydroxypropionate).

[0128]

[0129] Example 3

[0130] (1) Prepolymer manufacturing

[0131] 500 g (content 11.7%) of the 3-hydroxypropionic acid solution prepared in Preparation Example 1 was added to a 1000 ml glass reactor, and vacuum distillation was performed at a temperature of 40 to 50° C. to prepare a concentrated 3-hydroxypropionic acid aqueous solution (content 72%). 80 g of the 3-hydroxypropionic acid aqueous solution and 0.5 g of a p-toluenesulfonic acid (p-TSA) catalyst were added to an oil bath, and polymerization was performed at a temperature of 90° C. and a pressure of 70 torr for 2 hours to prepare a 3-hydroxypropionic acid prepolymer.

[0132] (2) Prepolymer washing

[0133] 3-Hydroxypropionic acid prepolymer was washed twice with double-distilled water at a temperature of 85°C. The washing solution was used in an amount twice the weight of the 3-hydroxypropionic acid prepolymer. The washed prepolymer and washing solution were separated into liquid and liquid fractions using a filter flask and a vacuum pump, thereby recovering the washed prepolymer.

[0134] (3) Polymer manufacturing

[0135] 30 g of the above prepolymer and 0.25 g of p-toluenesulfonic acid (p-TSA) catalyst were added to an oil bath, and polymerization was performed at a temperature of 90°C and a pressure of 1 torr for 30 hours to produce a polymer, i.e., poly(3-hydroxypropionate).

[0136]

[0137] Comparative Example 1

[0138] A prepolymer and a polymer were prepared in the same manner as in Example 1, except that the above (2) prepolymer washing process was not performed.

[0139]

[0140] Reference Example 1

[0141] (1) 3-hydroxypropionic acid tablets

[0142] The inorganic impurities remaining in the 3-hydroxypropionic acid solution prepared in the above Preparation Example 1 were purified by electrodialysis using an electrodialysis device from Innomeditech Co., Ltd. Specifically, the electrodialysis tank of the electrodialysis device used an Innomeditech Co., Ltd. L3 membrane as a cation and anion separation membrane, and was operated for 40 minutes in a constant voltage mode (20 V, 1 V per cell) of 20 cells. At this time, electrodialysis was performed until the electrical conductivity of the deionizing tank decreased to 10% of the initial conductivity of 100% of the deionizing tank, thereby recovering 3-hydroxypropionic acid.

[0143] (2) Prepolymer manufacturing

[0144] 600 g (content 10%) of the 3-hydroxypropionic acid solution prepared in Preparation Example 1 was added to a 1000 ml glass reactor, and concentrated 3-hydroxypropionic acid (content 72%) was prepared by vacuum distillation at a temperature of 40 to 50°C. An aqueous 3-hydroxypropionic acid solution (80 g, 72%) and 0.5 g of a p-toluenesulfonic acid (p-TSA) catalyst were added to an oil bath, and polymerization was performed at 90°C and 70 torr pressure for 2 hours to prepare a 3-hydroxypropionic acid prepolymer.

[0145] (3) Polymer manufacturing

[0146] The above prepolymer was polymerized by raising the temperature of the oil bath to 90°C without separate transfer and polymerizing at a pressure of 1 torr for 21 hours to produce a polymer, i.e., poly(3-hydroxypropinate).

[0147]

[0148] evaluation

[0149] 1. GPC (gel permeation chromatography) molecular weight evaluation

[0150] For each stage of the prepolymer and polymer manufactured in the above examples and comparative examples, the molecular weight was evaluated using equipment of the Water e2695 model and Agilent Plgel mixed c and b columns. The sample was prepared at 4 mg / ml with chloroform as a solvent and 20 μl was injected. The weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (PDI) were measured by gel permeation chromatography (GPC, Tosoh ECO SEC Elite), and the results are shown in Table 1 below. Meanwhile, if the molecular weight of the prepolymer was not measured, it was indicated as '-' in Table 1.

[0151] Solvent: chloroform (eluent)

[0152] Flow rate: 1.0 ml / min

[0153] Column temperature: 40℃

[0154] Standard: Polystyrene (corrected to a cubic function)

[0155]

[0156] 2. Measurement of element content

[0157] The element concentrations included in the prepolymers manufactured in Example 1 and Comparative Example 1 were measured using ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometry), and the results are shown in Table 1 below.

[0158] Specifically, the pretreatment was carried out by Prep. Acid Digestion. Approximately 0.05 g of the sample was accurately weighed into a Corning tube, and then 0.5 mL of nitric acid was added to the sample. After that, it was shaken overnight at room temperature to dissolve the sample. To promote the reaction of the sample, a small amount of hydrogen peroxide was added to dissolve the sample. When the sample was clearly and completely dissolved, it was diluted with ultrapure water to 10 mL to prepare the analysis sample. The undissolved components were removed with a 0.45 µm PTFE filter, and then the remaining filtrate was put into an ICP-OES instrument (AVIO 500, Perkin Elmer) to perform component analysis. On the other hand, when the elemental concentration was not measured, it was marked as '-' in Table 1.

[0159] <ICP-OES Analysis Conditions>

[0160] RF Power: 1300W

[0161] Torch Height: 15 mm

[0162] Plasma Gas Flow Rate: 15 L / min

[0163] Sample Gas Flow Rate: 0.8 L / min

[0164] Auxiliary Gas Flow Rate: 0.20 L / min

[0165] Pump Speed: 1.5 mL / min

[0166]

[0167] Elemental Concentration (ppm)Molecular Weight of Prepolymer (Da)Molecular Weight of Polymer (Da)CaNaPSKClMnMwPDIMnMwPDIExample 1<1014<1076<1072440>21561.37,42011,0401.49Example 2---------11,02021,0101.90Example 3---------9,96723,2202.32Comparative Example 13201850<1014213>563200212032301.52,1203,2301.52Reference Example 1---------10,55624,0102.27

[0168] Referring to Table 1 above, Example 1, which was polymerized into a prepolymer and then subjected to a washing process, had a low concentration of elements such as inorganic elements, confirming that a large amount of inorganic impurities such as inorganic compounds were removed from the starting material, the “organic acid composition containing inorganic compounds”, through the washing process. On the other hand, the prepolymer of Comparative Example 1, which was not washed, contained a large amount of elements such as inorganic elements, confirming that inorganic impurities such as inorganic compounds in the starting material, the “organic acid composition containing inorganic compounds”, still existed in the prepolymer. In addition, it was confirmed that Examples 1 to 3, in which a polymer was prepared by polymerizing a washed prepolymer, had a higher number average molecular weight and a weight average molecular weight than Comparative Example 1, in which a polymer was prepared by polymerizing an unwashed prepolymer. In addition, it was confirmed that Examples 1 to 3 had a polymer molecular weight similar to that of Reference Example 1, in which an organic acid was purified through an electrodialysis device.

Claims

1. A step of preparing an oligomer and / or prepolymer by polymerizing an organic acid composition containing an inorganic compound; and a step of washing the above oligomer and / or prepolymer with a washing solution; Method for producing organic acid prepolymer.

2. In paragraph 1, A method for producing an organic acid prepolymer, wherein the organic acid is at least one selected from the group consisting of lactic acid, 3-hydroxypropionic acid, butyric acid, acetic acid, propionic acid, succinic acid, and salts thereof.

3. In paragraph 1, A method for producing an organic acid prepolymer, wherein the purity of the organic acid in the organic acid composition containing the above inorganic compound is 90% or less.

4. In paragraph 1, A method for producing an organic acid prepolymer, wherein the organic acid composition containing the above inorganic compound comprises magnesium, calcium, sodium, phosphorus, sulfur, potassium, chlorine, salts or derivatives thereof, or mixtures thereof.

5. In paragraph 1, A method for producing an organic acid prepolymer, wherein the above oligomer and prepolymer each independently have a weight average molecular weight of 800 or more and 15,000 or less.

6. In paragraph 1, A method for producing an organic acid prepolymer, wherein the organic acid composition containing the above inorganic compound is recovered from a fermented liquid obtained by fermenting a strain having organic acid production ability.

7. In paragraph 1, Before the step of polymerizing the organic acid composition containing the above inorganic compound to produce an oligomer and / or prepolymer, A method for producing an organic acid prepolymer, further comprising a step of producing an organic acid fermentation liquid by fermenting a strain having organic acid production ability.

8. In paragraph 7, A method for producing an organic acid prepolymer, further comprising a step of mixing the above fermentation solution and an organic solvent to precipitate organic acid salt crystals.

9. In paragraph 8, A method for producing an organic acid prepolymer, further comprising the step of preparing a solution in which the organic acid salt crystals are dissolved and adding an acid to control the pH to 5 or lower.

10. In paragraph 1, A method for producing an organic acid prepolymer, wherein the above-mentioned washing solution is a solution containing water or a basic compound.

11. In paragraph 1, A method for producing an organic acid prepolymer, wherein the above washing is performed at a temperature of 50°C or higher and 300°C or lower.

12. In paragraph 1, After the step of washing the above oligomer and / or prepolymer with a washing solution, A method for producing an organic acid prepolymer, further comprising a step of separating the washed oligomer and / or prepolymer and the washing liquid into a solid or liquid.

13. A step of producing an oligomer and / or prepolymer by polymerizing an organic acid composition containing an inorganic compound; A step of washing the above oligomer and / or prepolymer with a washing solution; and A step of manufacturing a polymer by polymerizing the washed oligomer and / or prepolymer; comprising; Method for producing organic acid polymer.

14. In paragraph 13, A method for producing an organic acid polymer, wherein the polymer has a number average molecular weight of 7,000 or more.

15. In paragraph 13, A method for producing an organic acid polymer, wherein the polymer has a weight average molecular weight of 10,000 or more.

16. An organic acid composition containing an inorganic compound comprises a polymerized organic acid prepolymer, An organic acid prepolymer composition wherein the above inorganic compound is removed by washing.

17. In paragraph 16, An organic acid prepolymer composition wherein the organic acid prepolymer is a 3-hydroxypropionic acid prepolymer.

18. An organic acid polymer polymerized with an organic acid prepolymer composition according to Article 16.

19. In paragraph 18, The above organic acid polymer is an organic acid polymer, which is a 3-hydroxypropionic acid polymer.