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EP-4741509-A1 - METHOD FOR PREPARATION OF BRANCHED 3-HYDROXYPROPIONIC ACID PREPOLYMER AND ACRYLIC ACID

EP4741509A1EP 4741509 A1EP4741509 A1EP 4741509A1EP-4741509-A1

Abstract

The present invention relates to a method for preparing a fermentation broth by fermenting a strain capable of producing 3-hydroxypropionic acid in the presence of a polyol, and preparing a branched 3-hydroxypropionic acid prepolymer by polymerizing in the presence of the polyol, and a method for preparing bio-based acrylic acid by pyrolyzing the branched 3-hydroxypropionic acid prepolymer.

Inventors

  • NAM, Gibok
  • JEONG, DAE YOUN
  • LEE, JUNGYONG
  • LEE, HEE CHEON
  • CHOE, JAE HOON
  • BANG, YONGJU

Assignees

  • LG Chem, Ltd.

Dates

Publication Date
20260513
Application Date
20250529

Claims (14)

  1. A method for preparing branched 3-hydroxypropionic acid prepolymer, comprising: a step of fermenting a strain capable of producing 3-hydroxypropionic acid in the presence of a polyol to prepare a fermentation broth comprising the polyol and 3-hydroxypropionic acid: and a step of polymerizing the 3-hydroxypropionic acid in the presence of the polyol to prepare a branched 3-hydroxypropionic acid prepolymer.
  2. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 1, wherein the polymerization is carried out at a temperature of 70°C or more and 100°C or less.
  3. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 1, wherein the polyol comprises one or more selected from the group consisting of glycerol, pentaerythritol, 4-arm-poly(ethyleneglycol)n=2~10, di(trimethylolpropane), di(pentaerythritol), tri(pentaerythritol), xylitol, sorbitol, inositol, cholic acid, β-cyclodextrin and tetrahydroxyperylene.
  4. The method for preparing branched 3-hydroxypropionic acid prepolymer Claim 1, wherein the polyol is comprised in an amount of 0.01 wt% or more and 10.0 wt% or less based on 100 wt% of the 3-hydroxypropionic acid during the polymerization.
  5. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 1, further comprising a step of washing the branched 3-hydroxypropionic acid prepolymer.
  6. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 5, wherein the washing is carried out with a washing solution comprising water and/or a basic compound.
  7. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 5, wherein the washing is carried out at a temperature of 60°C or more and 90°C or less and for a time of 1 minute or more and 30 minutes or less.
  8. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 1, further comprising a step of separating the strain capable of producing 3-hydroxypropionic acid; and/or a step of generating and separating metal salt crystals by adding an acid to the fermentation broth comprising the polyol and 3-hydroxypropionic acid, after the step of fermenting a strain capable of producing 3-hydroxypropionic acid in the presence of a polyol to prepare a fermentation broth comprising the polyol and 3-hydroxypropionic acid.
  9. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 1, wherein the branched 3-hydroxypropionic acid prepolymer is represented by the following Formula 1: [Formula 1] R-[A-(B)n-C] k in the Formula 1, R is a functional group with a valence of 3 or more derived from polyol, A is a direct bond or a linking group derived from ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide or urethane, B is a substituent represented by the following Formula 2 or Formula 3, * is a part connected to A, k is an integer of 3 or more, n is an integer of 1 to 700, and C is a substituent represented by the following Formula 4 or Formula 5.
  10. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 9, wherein a ratio of the number of Formula 5 to a total of Formula 4 and Formula 5 is 5% or more.
  11. The method for preparing branched 3-hydroxypropionic acid prepolymer of Claim 1, wherein the branched 3-hydroxypropionic acid prepolymer has a weight average molecular weight of 1,800 or more and 90,000 or less.
  12. A method for preparing acrylic acid, comprising: a step of fermenting a strain capable of producing 3-hydroxypropionic acid in the presence of a polyol to prepare a fermentation broth comprising the polyol and 3-hydroxypropionic acid; a step of polymerizing the 3-hydroxypropionic acid in the presence of the polyol to prepare a branched 3-hydroxypropionic acid prepolymer; and a step of pyrolyzing the branched 3-hydroxypropionic acid prepolymer to prepare acrylic acid.
  13. The method for preparing acrylic acid of Claim 12, wherein the pyrolysis is carried out at a temperature of 170°C or more and 250°C or less.
  14. The method for preparing acrylic acid of Claim 12, wherein the acrylic acid has a content of bio-based carbon of 80 wt% or more as measured by the ASTM 6866-21 standard.

Description

FIELD OF THE INVENTION CROSS-REFERENCE TO RELATED APPLICATION(S) This application claims the benefit of Korean Patent Application No. 10-2024-0071883 filed on May 31, 2024, and Korean Patent Application No. 10-2025-0070312 filed on May 29, 2025 with the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety. The present invention relates to a method for preparing a high-purity branched 3-hydroxypropionic acid prepolymer and bio-based acrylic acid. BACKGROUND OF THE INVENTION Organic acids are commercially important chemicals with various uses in the food, cosmetic, pharmaceutical, and polymer industries. Representative organic acids include lactic acid, 3-hydroxypropionic acid (3-HP), and the like, and among them, 3-hydroxypropionic acid (3-HP) is a substance that can be utilized as a raw material for the preparation of acrylic acid, 1,3-propanediol, acrylamide, malonic acid, and biopolymers. The production of organic acids is largely carried out by two methods, a chemical method and a biological method, but the chemical method has been pointed out as being non-eco-friendly due to the high cost of starting materials and the generation of toxic substances during the production process, and thus, eco-friendly bio-processes are gaining attention. In the preparation of organic acids by microbial fermentation, since other by-products are also produced along with organic acids such as 3-hydroxypropionic acid during the process of fermenting microorganisms, purification processes such as electrodialysis and ion exchange resin are required to extract and separate the organic acids from the fermentation broth, and there is a problem that the process of performing these purification processes is long and the process cost is high. Accordingly, there is a need for a method to efficiently convert low-purity organic acids such as 3-hydroxypropionic acid containing by-products into raw materials for biopolymers and the like. SUMMARY OF THE INVENTION TECHNICAL PROBLEM The present invention relates to a method for preparing a high-molecular-weight and high-purity branched prepolymer from low-purity, unpurified 3-hydroxypropionic acid efficiently and at a low process cost, and preparing bio-based acrylic acid by pyrolyzing it. TECHNICAL SOLUTION In the present specification, there is provided a method for preparing branched 3-hydroxypropionic acid prepolymer, comprising a step of fermenting a strain capable of producing 3-hydroxypropionic acid in the presence of a polyol to prepare a fermentation broth comprising the polyol and 3-hydroxypropionic acid, and a step of polymerizing the 3-hydroxypropionic acid in the presence of the polyol to prepare a branched 3-hydroxypropionic acid prepolymer. In addition, in the present specification, there is provided a method for preparing acrylic acid, comprising a step of fermenting a strain capable of producing 3-hydroxypropionic acid in the presence of a polyol to prepare a fermentation broth comprising the polyol and 3-hydroxypropionic acid, a step of polymerizing the 3-hydroxypropionic acid in the presence of the polyol to prepare a branched 3-hydroxypropionic acid prepolymer, and a step of pyrolyzing the branched 3-hydroxypropionic acid prepolymer to prepare acrylic acid. Hereinafter, the method for preparing branched 3-hydroxypropionic acid prepolymer and acrylic acid according to a specific embodiment of the present invention will be described in more detail. The terminology used in this specification is used only to describe exemplary embodiments and is not intended to limit the present invention. A singular expression includes a plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that terms such as "comprising," "including," or "having" are intended to designate the presence of stated features, numbers, steps, components, or combinations thereof, and do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. Since the present invention may be variously modified and have various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed forms, and it should be understood to include all modifications, equivalents, and substitutes included in the spirit and technical scope of the present invention. In addition, unless the steps constituting the preparation method described in this specification are specified as being sequential or continuous, or there is another special class, one step constituting one preparation method and another step are not interpreted as being limited to the order described in the specification. Therefore, the order of the constituent steps of the preparation method can be changed within a range that can be easily understood by those skilled in the art,