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WO2021251049A1 - Procédé de production d'acide polyhydroxyalcanoïque et utilisation associée - Google Patents

Procédé de production d'acide polyhydroxyalcanoïque et utilisation associée Download PDF

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Publication number
WO2021251049A1
WO2021251049A1 PCT/JP2021/018084 JP2021018084W WO2021251049A1 WO 2021251049 A1 WO2021251049 A1 WO 2021251049A1 JP 2021018084 W JP2021018084 W JP 2021018084W WO 2021251049 A1 WO2021251049 A1 WO 2021251049A1
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Prior art keywords
pha
aqueous suspension
dispersant
unit
acid copolymer
Prior art date
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English (en)
Japanese (ja)
Inventor
智哉 西中
優 平野
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Kaneka Corp
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Kaneka Corp
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Priority to JP2022530072A priority Critical patent/JP7781749B2/ja
Publication of WO2021251049A1 publication Critical patent/WO2021251049A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/42—Hydroxy-carboxylic acids

Definitions

  • the present invention relates to a method for producing polyhydroxyalkanoic acid and its use.
  • PHA Polyhydroxyalkanoic acid
  • a step of separating and purifying PHA from the cells of microorganisms is required.
  • the step of separating and purifying PHA cells of PHA-containing microorganisms are disrupted or biological components other than PHA are solubilized, and then PHA is taken out from the obtained aqueous suspension.
  • separation operations such as centrifugation, filtration, and drying are performed.
  • a spray dryer, a fluidized bed dryer, a drum dryer, or the like is used for the drying operation, but a spray dryer is preferably used because the operation is simple.
  • the present inventor has used polyvinyl alcohol (PVA) as a dispersant before adjusting the pH of the aqueous suspension to 7 or less in order to prevent aggregation of PHA in the aqueous suspension having a pH of 7 or less.
  • PVA polyvinyl alcohol
  • PHA poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH) is known.
  • an object of the present invention is to provide a manufacturing method and a technique for utilizing the same, which can obtain PHA having a large particle size (for example, PHA powder) at a lower hot air temperature.
  • the polyhydroxybutyric acid copolymer (A) in the present invention may be a polymer composed of only 3-hydroxybutyrate units.
  • one aspect of the present invention is (a) a polyhydroxybutyric acid copolymer (A) having a composition ratio of 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit of 92/8 to 100/0.
  • a method for producing polyhydroxyalkanoic acid which comprises a step of preparing a turbid solution and (b) a step of spray-drying the aqueous suspension prepared in the step (a).
  • PHA having a large particle size (for example, PHA powder) at a lower hot air temperature.
  • the method for producing a polyhydroxyalkanoic acid according to an embodiment of the present invention has a composition ratio of (a) 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit.
  • the composition ratio of the polyhydroxybutyric acid copolymer (A) of 92/8 to 100/0 and the 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit is 75/25 to 91/9.
  • a step of preparing an aqueous suspension containing the copolymer (B) and having a pH of 7 or less, and (b) a step of spray-drying the aqueous suspension prepared in the above step (a). include.
  • "3-hydroxybutyrate” and “3-hydroxyhexanoate” may be referred to as "3HB” and "3HH", respectively.
  • the present inventor is proceeding with research and development on the production of P3HB3HH, and in order to produce P3HB3HH having a large particle size, which has been in increasing demand in recent years, the hot air temperature during spray drying is increased. I found that I needed to. However, increasing the hot air temperature requires more energy, which is not preferable in terms of energy efficiency. Further, by increasing the hot air temperature during spray drying, the possibility of damaging the P3HB3HH manufacturing equipment increases.
  • the present inventor has diligently studied a method for producing P3HB3HH having a large particle size while lowering the hot air temperature during spray drying.
  • P3HB and P3HB3HH or two different types of P3HB3HH (two types of P3HB3HH having different composition ratios of 3HB units and 3HH units)
  • the hot air temperature during spray drying is lowered and the particle size is large.
  • P3HB3HH can be obtained.
  • the polyhydroxybutyrate copolymer (A) having a 3HB unit / 3HH unit of 92/8 to 100/0 and the polyhydroxybutyric acid copolymer having a 3HB unit / 3HH unit of 75/25 to 91/9 It has been found for the first time that P3HB3HH having a large particle size can be obtained by combining with the polymer (B) while lowering the hot air temperature during spray drying.
  • PHA having a large particle size for example, PHA powder
  • PHA powder PHA having a large particle size
  • Step (a)) In the step (a) in the present production method, an aqueous suspension containing the polyhydroxybutyric acid copolymer (A) and the polyhydroxybutyric acid copolymer (B) and having a pH of 7 or less is prepared.
  • the polyhydroxybutyric acid copolymer (A) and the polyhydroxybutyric acid copolymer (B) are present in a dispersed state in the aqueous medium.
  • the polyhydroxybutyrate copolymer (A) is P3HB or P3HB3HH.
  • the polyhydroxybutyrate copolymer (B) is P3HB3HH.
  • both the polyhydroxybutyric acid copolymer (A) and the polyhydroxybutyric acid copolymer (B) correspond to PHA.
  • the aqueous suspension containing at least the polyhydroxybutyric acid copolymer (A) and / or the polyhydroxybutyric acid copolymer (B) is simply abbreviated as "PHA aqueous suspension”. There is.
  • P3HB poly (3-hydroxybutyrate)
  • P3HB3HH poly (3-hydroxybutyrate-co)
  • P3HB3HH -3-Hydroxyhexanoate
  • P3HB3HH is a copolymer of 3-hydroxybutyric acid and 3-hydroxycaproic acid.
  • P3HB3HH can change the melting point and crystallinity by changing the composition ratio of the repeating unit, and as a result, can change the physical properties such as Young's modulus and heat resistance.
  • P3HB3HH can impart physical characteristics between polypropylene and polyethylene.
  • P3HB3HH is a plastic that is industrially easy to produce and is physically useful.
  • the polyhydroxybutyric acid copolymer (A) has a composition ratio of 3HB units / 3HH units of 92/8 to 100/0.
  • the balance between flexibility and strength of PHA produced by the present production method is well maintained. Can be done.
  • the composition ratio of 3HB unit / 3HH unit in the polyhydroxybutyric acid copolymer (A) is preferably 92/8 to 99/1, preferably 93/7 to 99/1. More preferably, it is 94/6 to 99/1.
  • the polyhydroxybutyrate copolymer (A) has a composition ratio of 3HB units / 3HH units of 100/0, that is, only 3HB units. It is particularly preferable that the configuration is composed of.
  • the polyhydroxybutyrate copolymer (B) has a composition ratio of 3HB units / 3HH units of 75/25 to 91/9. Since the polyhydroxybutyric acid copolymer (B) has a large composition ratio of 3 HH units, the melting temperature is low. Therefore, in the step (b) of spray-drying the PHA aqueous suspension in the present production method, the polyhydroxybutyric acid copolymer (B) is in a molten state even when the hot air temperature is low.
  • the polyhydroxybutyric acid copolymer (B) in a molten state functions as a binder for aggregating the particles (powder) of the polyhydroxybutyric acid copolymer (A). Therefore, in this production method, even when the hot air temperature is low, the polyhydroxybutyrate copolymer (A) particles (powder) are in a fused state as a binder and have the polyhydroxybutyrate copolymer weight. It is possible to produce a PHA having a large particle size, which is aggregated through the coalescence (B).
  • the composition ratio of 3HB unit / 3HH unit in the polyhydroxybutyrate copolymer (B) is preferably 80/20 to 91/9, and is preferably 83/17 to 90 /. It is more preferably 10 and even more preferably 85/15 to 90/10.
  • the content of the polyhydroxybutyric acid copolymer (B) in the PHA aqueous suspension is 1 to 30 with respect to the content of the polyhydroxybutyric acid copolymer (A). It is preferably a part by weight.
  • the binder can be used as a binder.
  • the content of the functional polyhydroxybutyrate copolymer (B) can be sufficiently ensured, and as a result, PHA having a larger particle size can be suitably produced at a lower temperature.
  • the content of the polyhydroxybutyric acid copolymer (B) in the PHA aqueous suspension is 2 parts by weight or more with respect to the content of the polyhydroxybutyric acid copolymer (A). More preferably, it is more preferably 5 parts by weight or more.
  • the content of the polyhydroxybutyric acid copolymer (B) in the PHA aqueous suspension being 30 parts by weight or less with respect to the content of the polyhydroxybutyric acid copolymer (A).
  • the balance between flexibility and strength of PHA can be improved.
  • the content of the polyhydroxybutyric acid copolymer (B) in the PHA aqueous suspension is 25 parts by weight or less with respect to the content of the polyhydroxybutyric acid copolymer (A). More preferably, it is more preferably 20 parts by weight or less.
  • the step (a) preferably includes the following steps (a1) and (a2).
  • Step (a1) The aqueous suspension containing the polyhydroxybutyric acid copolymer (A) and the aqueous suspension containing the polyhydroxybutyric acid copolymer (B) are mixed to form a PHA aqueous suspension.
  • -Step (a2) A step of adjusting the pH of the PHA aqueous suspension to 7 or less.
  • the order in which the steps (a1) and the steps (a2) are carried out is not particularly limited.
  • the order in which the steps (a1) and (a2) are carried out is the step (a1) from the viewpoint that aggregation of PHA in the step (a2) is suppressed and an aqueous suspension having more excellent dispersion stability of PHA can be obtained. ), It is preferable to carry out the step (a2).
  • the aqueous suspension containing the polyhydroxybutyric acid copolymer (A) and the aqueous suspension containing the polyhydroxybutyric acid copolymer (B) used as a starting material are not particularly limited.
  • the aqueous suspension comprises, for example, a culture step of culturing a microorganism capable of producing PHA in cells, and a purification step of decomposing and / or removing substances other than PHA after the culture step. Can be obtained by
  • an aqueous suspension containing the polyhydroxybutyric acid copolymer (A) and an aqueous suspension containing the polyhydroxybutyric acid copolymer (B) are obtained before the step (a). It may be included.
  • the microorganism used in the step is not particularly limited as long as it is a microorganism capable of producing PHA in the cell. For example, microorganisms isolated from nature, microorganisms deposited in a depository institution for strains (eg, IFO, ATCC, etc.), or mutants or transformants that can be prepared from them can be used.
  • the genus Cupriavidus the genus Alcaligenes, the genus Ralstonia, the genus Pseudomonas, the genus Bacillus, the genus Bacillus, the genus Azotobacter, the genus Azotobacter.
  • bacteria of the genus include bacteria of the genus (Aeromonas).
  • microorganisms belonging to the genus Aeromonas, Alcaligenes, Ralstonia, or Cupriavidus are preferable.
  • Alcaligenes lipolytica, Alcaligenes ratus, Aeromonas cavier (A. cav). Strains such as iae), Aeromonas hydrophila, and Cupriavidus necator are more preferred, with cupriavidus necator being the most preferred.
  • the target PHA synthase gene and / or a variant thereof can be applied to the microorganism.
  • the transformant obtained by introduction can also be used.
  • the PHA synthase gene used for producing such a transformant is not particularly limited.
  • As the synthase gene a gene for PHA synthase derived from Aeromonas cavier is preferable.
  • the culture method for example, the method described in Japanese Patent Application Laid-Open No. 05-93049 is used.
  • the aqueous suspension containing the polyhydroxybutyric acid copolymer (A) and the aqueous suspension containing the polyhydroxybutyric acid copolymer (B) are of the same bacterial species and It can be obtained from cells having different gene mutations by the same culture method.
  • the method described in the international publication "WO2019 / 142717" can be mentioned.
  • a purification step for decomposing and / or removing impurities other than PHA is usually performed. Can be carried out.
  • physical treatment, chemical treatment, biological treatment and the like which can be considered by those skilled in the art can be applied without particular limitation, and for example, it is described in International Publication "WO2010 / 067543".
  • the purification method of is preferably applicable.
  • the amount of impurities remaining in the final product is generally determined by the above purification step, it is preferable to reduce these impurities as much as possible.
  • impurities may be mixed as long as the physical properties of the final product are not impaired, but when high-purity PHA is required for medical applications, etc., impurities can be reduced as much as possible.
  • the amount of protein in the aqueous suspension of PHA can be mentioned.
  • the amount of the protein is preferably 30,000 ppm or less, more preferably 15,000 ppm or less, still more preferably 10,000 ppm or less, and most preferably 7500 ppm or less per PHA weight.
  • the purification means is not particularly limited. As the purification means, for example, the above-mentioned known method can be applied.
  • the concentration of the organic solvent compatible with water is not particularly limited as long as it is equal to or less than the solubility of the organic solvent used in water.
  • the organic solvent compatible with water is not particularly limited. Examples of the organic solvent compatible with water include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, pentanol, hexanol, and heptanol; acetone.
  • Ketones such as methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide and acetamide; dimethylsulfoxide, pyridine, piperidine and the like.
  • methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, acetonitrile, propionitrile and the like are preferable because they are easy to remove.
  • aqueous medium constituting the PHA aqueous suspension may contain other solvents, bacterial cell-derived components, compounds generated during purification, etc., as long as the essence of the present invention is not impaired.
  • the aqueous medium constituting the PHA aqueous suspension in the present production method contains water.
  • the content of water in the aqueous medium is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 30% by weight or more, and particularly preferably 50% by weight or more.
  • the aqueous suspension in one embodiment of the present invention may contain a dispersant. That is, in the step (a) in one embodiment of the present invention, an aqueous suspension further containing a dispersant in addition to the polyhydroxybutyric acid copolymer (A) and the polyhydroxybutyric acid copolymer (B). It may be a step of preparing.
  • the dispersant is used in one embodiment of the present invention, it is preferable to add the dispersant to the PHA aqueous suspension in the step (a1).
  • the PHA aqueous suspension in one embodiment of the present invention can suitably improve the productivity and thermal stability of PHA by containing a dispersant.
  • the dispersant is not particularly limited.
  • examples of the dispersant include an alkylene oxide-based dispersant.
  • the dispersant may be one kind or two or more kinds.
  • Patent Document 1 described above uses polyvinyl alcohol (PVA) as a dispersant, and shows the result that the particle size of PHA is increased due to the binder effect of the PVA.
  • PVA polyvinyl alcohol
  • PHA having a large particle size can be obtained at a lower hot air temperature without causing the problem of shaft adhesion.
  • the dispersant can suitably prevent agglutination of PHA when adjusting the pH of the aqueous suspension of PHA to 7 or less, and is an extruder for powder processing.
  • An alkylene oxide-based dispersant is preferable in terms of being able to suitably suppress the adhesion of the powder to the shaft.
  • the alkylene oxide-based dispersant is not particularly limited as long as it exhibits the above effects.
  • the alkylene oxide-based dispersant is composed of a block of poly (ethylene oxide) (PEO) and a block of poly (propylene oxide) (PPO), and is preferably in the form of PEO-PPO-PEO.
  • poly (ethylene oxide) (PEO) block means a polymer portion formed by polymerizing ethylene oxide (EO) in the structure of an alkylene oxide-based dispersant.
  • poly (propylene oxide) (PPO) block means a polymer portion formed by polymerizing propylene oxide (PO) in the structure of an alkylene oxide-based dispersant.
  • the viscosity of the aqueous suspension is kept low and the PHA (for example, for example) is highly productive. PHA powder) can be produced.
  • the range of PEO molecular weight and PEO molecular weight / PPO molecular weight in the alkylene oxide-based dispersant is preferably the following combination.
  • PEO molecular weight may be referred to as "EO molecular weight”
  • PPO molecular weight may be referred to as "PO molecular weight”.
  • the PEO molecular weight in the alkylene oxide-based dispersant may be 1500 or more, preferably 1750 or more, and more preferably 2000 or more.
  • the upper limit of the PEO molecular weight in the alkylene oxide-based dispersant is, for example, 30,000 or less, preferably 25,000 or less, and more preferably 20,000 or less.
  • the PEO molecular weight / PPO molecular weight in the alkylene oxide-based dispersant is preferably 0.5 or more, more preferably 0.6 or more, and 0.7 or more. Is even more preferable.
  • the upper limit of the PEO molecular weight / PPO molecular weight is preferably 5.0 or less, more preferably 4.8 or less, and further preferably 4.5 or less.
  • the alkylene oxide-based dispersant has hydrophilicity and the alkylene oxide-based dispersant is dispersed. Since the number of molecules increases with respect to the added weight of the agent, it is easy to maintain the dispersibility of the aqueous suspension.
  • the alkylene oxide-based dispersant has a PEO molecular weight of 1500 or more and a PEO molecular weight / PPO molecular weight of 0.5 to 5.0.
  • the alkylene oxide-based dispersant preferably has at least one PEO block having a molecular weight of 750 or more, and more preferably at least two or more.
  • the upper limit of the number of the PEO blocks in the alkylene oxide-based dispersant is not particularly limited, and is, for example, 4 or less, preferably 3 or less. When the number of PEO blocks is within the above range, the alkylene oxide-based dispersant has hydrophilicity.
  • the PPO molecular weight in the alkylene oxide-based dispersant is not particularly limited.
  • the PPO molecular weight in the alkylene oxide-based dispersant is, for example, 500 or more, preferably 1500 or more.
  • the upper limit of the PPO molecular weight in the alkylene oxide-based dispersant is, for example, 6700 or less, preferably 6250 or less.
  • the alkylene oxide-based dispersant has hydrophobicity.
  • the number of PPO blocks in the alkylene oxide-based dispersant is not particularly limited as long as the above effects are exhibited.
  • the number of PPO blocks in the alkylene oxide-based dispersant may be one or a plurality (for example, 2, 3, 4).
  • the alkylene oxide-based dispersant is, for example, a compound represented by the following formula (1).
  • X is, for example, 17 to 340, preferably 20 to 285, and more preferably 22 to 226.
  • X is 340 or less, the number of molecules increases with respect to the weight of the alkylene oxide-based dispersant added, so that the dispersibility of the aqueous suspension can be easily maintained, and when X is 17 or more, it is represented by the formula (1).
  • the compound has hydrophilicity.
  • Y is, for example, 8 to 115, preferably 10 to 110, and more preferably 24 to 107. When Y is 115 or less, the compound represented by the formula (1) is easily dissolved in water, and when Y is 8 or more, the compound represented by the formula (1) has hydrophobicity. ..
  • Z is, for example, 17 to 340, preferably 20 to 285, and more preferably 22 to 226.
  • Z is 340 or less, the number of molecules increases with respect to the weight of the alkylene oxide-based dispersant added, so that the dispersibility of the aqueous suspension can be easily maintained, and when Z is 17 or more, it is represented by the formula (1).
  • the compound has hydrophilicity.
  • X + Z the sum of X and Z (hereinafter, may be referred to as “X + Z”) is, for example, 34 to 680, preferably 40 to 570, and more preferably. Is 44 to 452.
  • X + Z is 680 or less, the number of molecules increases with respect to the weight of the alkylene oxide-based dispersant added, so that the dispersibility of the aqueous suspension can be easily maintained, and when X is 34 or more, it is represented by the formula (1).
  • the compound has hydrophilicity.
  • the alkylene oxide-based dispersant used in the step (a) (particularly, the step (a1)) of the present production method is not particularly limited.
  • the alkylene oxide-based dispersant for example, a commercially available product can be used. Examples of commercially available products include Pluronic 10400 (manufactured by BASF), Pluronic 10500 (manufactured by BASF), Genapol PF80 (manufactured by Clariant), Unilube DP60-600B (manufactured by NOF), and Unilube DP60-950B (manufactured by NOF).
  • Pronon 208 manufactured by NOF Corporation
  • Epan U105 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Epan U108 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Epan 750 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • the amount of the dispersant added to the aqueous suspension in the step (a) (particularly, the step (a1)) of the present production method is not particularly limited.
  • the amount of the dispersant added is 0.I. 1 to 20 parts by weight is preferable, 0.5 to 10 parts by weight is more preferable, and 0.75 to 5 parts by weight is further preferable.
  • the addition amount of the dispersant within the above range, the dispersion stability of PHA in the aqueous PHA suspension can be further improved, and spray drying can be efficiently performed, and as a result, the productivity and thermal stability of PHA can be achieved. There is a tendency that the property can be improved more preferably.
  • the PHA aqueous suspension before being subjected to the step (a) of the present production method usually has a pH of more than 7 by undergoing the above purification step. Therefore, the PHA aqueous suspension obtained in the step (a1) of this production method has a pH exceeding 7. Therefore, the pH of the PHA aqueous suspension is adjusted to 7 or less by the step (a) (particularly, the step (a2)) of the present production method.
  • the adjustment method is not particularly limited. Examples of the adjustment method include a method of adding an acid.
  • the acid is not particularly limited.
  • the acid may be either an organic acid or an inorganic acid, and may or may not be volatile. More specifically, as the acid, for example, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and the like can be used.
  • the upper limit of the pH of the PHA aqueous suspension adjusted in the above adjustment step from the viewpoint of reducing the coloring when the PHA is heated and melted, and from the viewpoint of ensuring the stability of the molecular weight during heating and / or drying. , 7 or less, preferably 5 or less, and more preferably 4 or less.
  • the lower limit of pH is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, from the viewpoint of acid resistance of the container.
  • an aqueous suspension containing the polyhydroxybutyric acid copolymer (A) and the polyhydroxybutyric acid copolymer (B) and having a pH of 7 or less is provided.
  • the concentration of PHA in the aqueous suspension of PHA obtained by the step (a) of the present production method is economically advantageous in terms of drying utility and improves productivity, so that it is preferably 30% by weight or more, preferably 40% by weight. % Or more is more preferable, and 50% by weight or more is further preferable.
  • the concentration of PHA in the aqueous suspension of PHA means the total concentration of the polyhydroxybutyric acid copolymer (A) and the concentration of the polyhydroxybutyric acid copolymer (B). Further, the upper limit of the concentration of PHA is close-packed, and sufficient fluidity may not be ensured. Therefore, 65% by weight or less is preferable, and 60% by weight or less is more preferable.
  • the method for adjusting the concentration of PHA is not particularly limited.
  • Examples of the method for adjusting the concentration of PHA include a method of adding an aqueous medium and a method of removing a part of the aqueous medium (for example, by centrifuging and then removing the supernatant).
  • the adjustment of the PHA concentration may be carried out at any stage of the step (a), or may be carried out at a stage before the step (a).
  • the concentration of polyhydroxyalkanoic acid in the aqueous suspension prepared in step (a) is 30% by weight or more and 65% by weight or less.
  • volume median diameter of PHA in the aqueous suspension of PHA obtained by the step (a) of the present production method is the volume median diameter of the primary particles of PHA (hereinafter referred to as "volume median diameter"). , 50 times or less, more preferably 20 times or less, still more preferably 10 times or less. Since the volume median diameter of PHA is 50 times or less the diameter of the primary particle, the PHA aqueous suspension exhibits better fluidity, so that the subsequent step (b) can be carried out with high efficiency. As a result, the productivity of PHA tends to be further improved.
  • the volume median diameter of PHA is preferably 0.5 to 5 ⁇ m, more preferably 1 to 4.5 ⁇ m, and 1 to 4 ⁇ m, for example, from the viewpoint of achieving excellent fluidity. More preferred.
  • the volume median diameter of PHA is measured, for example, by using a laser diffraction / scattering particle size distribution measuring device LA-950 manufactured by HORIBA.
  • the volume median diameter of PHA can be used as an index of the dispersed state of PHA in the aqueous suspension of PHA.
  • the method for adjusting the volume median diameter of the PHA is not particularly limited.
  • a known means (stirring or the like) can be applied.
  • a PHA aqueous suspension whose dispersed state has collapsed due to exposure to acidic conditions for example, when the step (a2) is carried out before the step (a1)
  • those skilled in the art for a PHA aqueous suspension whose dispersed state has collapsed due to exposure to acidic conditions (for example, when the step (a2) is carried out before the step (a1)).
  • the PHA in the aqueous suspension of PHA is returned to the dispersed state (for example, the state having the volume median diameter of PHA described above). You can also.
  • the PHA aqueous suspension prepared in the step (a) is spray-dried.
  • the spray drying method include a method in which a PHA aqueous suspension is supplied into a dryer in the form of fine droplets and dried while being in contact with hot air in the dryer.
  • the method (atomizer) for supplying the PHA aqueous suspension in the form of fine droplets into the dryer is not particularly limited.
  • Examples of the method of supplying the PHA aqueous suspension in the form of fine droplets into the dryer include known methods such as a method using a rotating disk and a method using a nozzle.
  • the contact method between the droplet and the hot air in the dryer is not particularly limited. Examples of the contact method between the droplet and the hot air in the dryer include a parallel flow type, a countercurrent type, and a method in which these are used in combination.
  • the drying temperature at the time of spray drying in the step (b) may be a temperature at which most of the aqueous medium can be removed from the droplets of the PHA aqueous suspension.
  • the drying temperature can be appropriately set under conditions that can be dried to the desired moisture content and that quality deterioration (molecular weight reduction, color tone reduction, etc.), melting, etc. are not caused as much as possible.
  • the hot air temperature is, for example, 200 ° C. or lower, preferably 180 ° C. or lower, and more preferably 160 ° C. or lower.
  • the "hot air temperature” means the temperature of the hot air blown into the spray dryer used in the step (b).
  • the exhaust air temperature is, for example, 114 ° C. or lower, preferably 112 ° C. or lower, and more preferably 110 ° C. or lower.
  • the “exhaust air temperature” is the temperature of the exhaust gas when it is discharged from the spray dryer, and can be read as "the particle temperature of PHA" which is discharged.
  • the hot air temperature or the exhaust air temperature is equal to or lower than the above-mentioned temperature, the amount of energy required for spray drying can be reduced, and as a result, the amount of energy required for producing the PHA can be suitably reduced. can. This also prevents damage to the PHA manufacturing equipment.
  • the lower limit of the hot air temperature is not particularly limited.
  • the lower limit of the hot air temperature is, for example, 120 ° C. or higher, preferably 130 ° C. or higher.
  • the lower limit of the exhaust air temperature is not particularly limited.
  • the lower limit of the exhaust air temperature is, for example, 90 ° C. or higher, preferably 95 ° C. or higher.
  • the amount of hot air in the dryer can also be set as appropriate according to, for example, the size of the dryer.
  • the present production method may include, after the step (b), a step of further drying the obtained PHA (PHA powder or the like) (for example, a step of subjecting to vacuum drying or the like).
  • the present production method may include other steps (for example, a step of adding various additives to a PHA aqueous suspension).
  • the polyhydroxyalkanoic acid powder according to one embodiment of the present invention is a polyhydroxybutyric acid having a composition ratio of 3HB units / 3HH units of 92/8 to 100/0. It contains a copolymer (A), a polyhydroxybutyric acid copolymer (B) having a composition ratio of 3HB units / 3HH units of 75/25 to 91/9, and a dispersant.
  • the median particle size of this PHA powder is not particularly limited.
  • the median particle size of the PHA powder is preferably 40 to 120 ⁇ m, more preferably 42 to 100 ⁇ m, from the viewpoint of achieving excellent fluidity.
  • the median particle size of the PHA powder is measured by the method described in Examples.
  • the content of the dispersant in the PHA powder is not particularly limited.
  • the content of the dispersant in the PHA powder is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and 0. More preferably, 75 to 5 parts by weight.
  • the PHA powder may contain various components generated or not removed in the process of the present production method as long as the effect of the present invention is exhibited.
  • This PHA powder can be used for various purposes such as paper, film, sheet, tube, plate, rod, container (for example, bottle container, etc.), bag, parts, etc.
  • one embodiment of the present invention is as follows. ⁇ 1> (a) The polyhydroxybutyric acid copolymer (A) having a composition ratio of 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit of 92/8 to 100/0 and 3-hydroxybutyrate unit. A step of preparing an aqueous suspension containing the polyhydroxybutyric acid copolymer (B) having a composition ratio of / 3-hydroxyhexanoate unit of 75/25 to 91/9 and having a pH of 7 or less. , And (b) a step of spray-drying the aqueous suspension prepared in the above step (a), a method for producing polyhydroxyalkanoic acid.
  • the content of the polyhydroxybutyrate copolymer (B) in the aqueous suspension is 1 to 30 parts by weight with respect to the content of the polyhydroxybutyrate copolymer (A).
  • ⁇ 4> The method for producing a polyhydroxyalkanoic acid according to any one of ⁇ 1> to ⁇ 3>, wherein the aqueous suspension further contains a dispersant.
  • the dispersant is an alkylene oxide-based dispersant.
  • the alkylene oxide-based dispersant is composed of a block of poly (ethylene oxide) (PEO) and a block of poly (propylene oxide) (PPO), and is in the form of PEO-PPO-PEO, ⁇ 4> or ⁇ .
  • the dispersant is an alkylene oxide-based dispersant.
  • the dispersant is an alkylene oxide-based dispersant.
  • the composition ratio of the 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit of the polyhydroxybutyric acid copolymer (A) is 92/8 to 99/1.
  • P3HB3HH is used as “PHA”
  • PHA can be read as “P3HB3HH”.
  • the average particle size of the PHA powder after spray drying obtained by this production method was measured by the following method.
  • the average particle size was measured using a laser diffraction / scattering type particle size distribution measuring device LA-950 (HORIBA).
  • LA-950 laser diffraction / scattering type particle size distribution measuring device LA-950 (HORIBA).
  • 0.05 g of sodium dodecyl sulfate, which is a surfactant was added to 20 ml of ion-exchanged water as a dispersant to obtain an aqueous surfactant solution.
  • 0.2 g of the resin particle group to be measured was added to the surfactant aqueous solution, and the resin particle group was dispersed in the surfactant aqueous solution to obtain a dispersion liquid for measurement.
  • the prepared dispersion was introduced into the laser diffraction / scattering type particle size distribution measuring device and measured.
  • composition ratio of 3HB unit / 3HH unit The composition ratio of 3HB units / 3HH units in PHA was measured by the method described in Japanese Patent Publication No. 05-93049.
  • Example 1 (Preparation of cell culture solution)
  • the Ralstonia utrofa KNK-005 strain described in paragraph [0049] of International Publication No. 2008/010296 is cultured by the method described in paragraphs [0050] to [0053] of the same document, and cells containing PHA are obtained.
  • a cell culture solution containing the cells was obtained.
  • Ralstonia eutropha is now classified as Cupriavidus necator.
  • the composition ratio of the repeating unit of PHA contained in the cells was 92/8 to 95/5 (mol / mol).
  • the cell culture solution obtained above was heated and stirred at an internal temperature of 60 to 80 ° C. for 20 minutes to perform sterilization.
  • composition ratio of PHA repeating units is 8/20 to 91/9 (mol / mol) by 52.8 weight.
  • % PHA aqueous suspension (hereinafter referred to as “PHA aqueous suspension (B)”) was prepared.
  • the PHA aqueous suspension (A) obtained above and the PHA aqueous suspension (B) were mixed to obtain a mixed solution 1.
  • the amount of the PHA aqueous suspension (B) added to 100 parts by weight of the PHA aqueous suspension (A) was 5 parts by weight.
  • Water is added to adjust the concentration of the mixed solution so that the concentration of PHA, which is the solid content of the mixed solution 1, is 32.8% by weight, and then the ethylene oxide / propylene oxide copolymer nonionic.
  • Dispersant polyethylene oxide molecular weight 8000, polypropylene oxide molecular weight 2000, trade name Pronon 208
  • 1.0 phr 1 part by weight based on 100 parts by weight of PHA present in the aqueous suspension
  • water was further added to the mixture 2 to adjust the solid content concentration to 30% by mass to obtain the mixture 3.
  • 0.4 ml of 10 wt% sulfuric acid was added to 100 g of the mixture 3 to obtain a PHA aqueous suspension having a pH of 3.0.
  • the obtained PHA aqueous suspension was spray-dried by a rotary atomizer type spray dryer (Mobile Minor) manufactured by GEA (hot air temperature: 170 ° C., exhaust air temperature: 100 ° C., rotary atomizer rotation speed: 10000 rpm. ), PHA powder was obtained.
  • the median particle size of the obtained PHA powder was 44.3 ⁇ m.
  • Example 2 PHA powder was obtained in the same manner as in Example 1 except that the amount of the PHA aqueous suspension (B) added was 10 parts by weight. The median particle size of the obtained PHA powder was 45.4 ⁇ m.
  • Example 3 PHA powder was obtained in the same manner as in Example 1 except that the amount of the PHA aqueous suspension (B) added was 15 parts by weight. The median particle size of the obtained PHA powder was 58.3 ⁇ m.
  • Example 4 PHA powder was obtained by the same method as in Example 1 except that the amount of the PHA aqueous suspension (B) added was 20 parts by weight. The median particle size of the obtained PHA powder was 73.4 ⁇ m.
  • Example 1 PHA powder was obtained in the same manner as in Example 1 except that the PHA aqueous suspension (B) was not added.
  • the median particle size of the obtained PHA powder was 39.9 ⁇ m.
  • Example 5 By the same operation as in Example 1 except that the composition ratio of the repeating unit of PHA (composition ratio of 3HB unit / 3HH unit) was 96/4 to 99/1 (mol / mol), the solid content concentration was 52.8 weight by weight. % PHA aqueous suspension was prepared. Hereinafter, this PHA aqueous suspension is shown as a PHA aqueous suspension (C). The PHA aqueous suspension was prepared in the same manner as in Example 1 except that the amount of the PHA aqueous suspension (B) added to the PHA aqueous suspension (C) was 20 parts by weight.
  • PHA powder was obtained under the conditions of hot air temperature 180 ° C., exhaust air temperature: 105 ° C., and rotary atomizer rotation speed 10000 rpm.
  • the median particle size of the obtained PHA powder was 58.8 ⁇ m.
  • the polyhydroxybutyrate having a composition ratio of 3HB units / 3HH units as PHA is 92/8 to 100/0. Obtained by spray-drying an aqueous suspension containing the polyhydroxybutyrate copolymer (B) having a composition ratio of 3HB units / 3HH units of 75/25 to 91/9 in addition to the copolymer (A).
  • the PHA powder is obtained by spray-drying an aqueous suspension containing only the polyhydroxybutyrate copolymer (A) having a composition ratio of 3HB units / 3HH units as PHA of 92/8 to 100/0. It was found that the particle size (media particle size) was larger than that of the powder under the same drying conditions.
  • the particle size of the obtained PHA (for example, PHA powder) is made larger than that in the method using an aqueous suspension containing only the polyhydroxybutyrate copolymer (A) as PHA. be able to.
  • PHA having a large particle size (for example, PHA powder) can be produced even if the hot air temperature in spray drying is low.
  • this production method can produce PHA having a large particle size (for example, PHA powder) at a lower hot air temperature, it can be advantageously used in the production of PHA. Further, the PHA powder or the like obtained by this production method can be suitably used in agriculture, fisheries, forestry, horticulture, medicine, sanitary goods, clothing, non-clothing, packaging, automobiles, building materials, and other fields. ..

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Abstract

La présente invention vise à fournir un procédé de production permettant d'obtenir un PHA ayant une grande taille de particules (par exemple, une poudre de PHA) à une température d'air moins élevée. L'invention concerne par conséquent un procédé de production d'un PHA, ledit procédé comprenant une étape de séchage par pulvérisation d'une suspension aqueuse qui contient un copolymère d'acide polyhydroxybutyrique (A) ayant un rapport de composition unité 3HB/unité 3HH de 92/8 à 100/0 et un copolymère d'acide polyhydroxybutyrique (B) ayant un rapport de composition unité 3HB/unité 3HH de 75/25 à 91/9, et une étape (b) de séchage par pulvérisation de la suspension aqueuse préparée à l'étape (a).
PCT/JP2021/018084 2020-06-09 2021-05-12 Procédé de production d'acide polyhydroxyalcanoïque et utilisation associée Ceased WO2021251049A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023149511A1 (fr) * 2022-02-07 2023-08-10 株式会社カネカ Poudre de poly(acide hydroxyalcanoïque) et son utilisation
WO2023181993A1 (fr) * 2022-03-23 2023-09-28 株式会社ダイセル Particules aplaties biodégradables, composition cosmétique et procédé de production de particules aplaties biodégradables
WO2024029220A1 (fr) * 2022-08-05 2024-02-08 株式会社カネカ Procédé de production de polyhydroxyalcanoate et son utilisation
WO2024075597A1 (fr) 2022-10-03 2024-04-11 株式会社カネカ Procédé de fabrication d'un mélange copolymère d'acide polyhydroxyalcanoïque, et micro-organisme transformé

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JP2000502375A (ja) * 1995-12-12 2000-02-29 モンサント・カンパニー ポリヒドロキシアルカノエートの水中分散系
JP2004107413A (ja) * 2002-09-17 2004-04-08 Mitsui Chemicals Inc 可塑剤含有ポリ乳酸系樹脂水分散体
JP2004250629A (ja) * 2003-02-21 2004-09-09 Kanegafuchi Chem Ind Co Ltd ポリヒドロキシアルカン酸の製造方法
JP2011140656A (ja) * 2003-02-21 2011-07-21 Metabolix Inc Ｐｈａブレンド
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Publication number Priority date Publication date Assignee Title
WO2023149511A1 (fr) * 2022-02-07 2023-08-10 株式会社カネカ Poudre de poly(acide hydroxyalcanoïque) et son utilisation
WO2023181993A1 (fr) * 2022-03-23 2023-09-28 株式会社ダイセル Particules aplaties biodégradables, composition cosmétique et procédé de production de particules aplaties biodégradables
WO2024029220A1 (fr) * 2022-08-05 2024-02-08 株式会社カネカ Procédé de production de polyhydroxyalcanoate et son utilisation
WO2024075597A1 (fr) 2022-10-03 2024-04-11 株式会社カネカ Procédé de fabrication d'un mélange copolymère d'acide polyhydroxyalcanoïque, et micro-organisme transformé

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