WO2021176941A1 - ポリヒドロキシアルカン酸の製造方法およびその利用 - Google Patents

ポリヒドロキシアルカン酸の製造方法およびその利用 Download PDF

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WO2021176941A1
WO2021176941A1 PCT/JP2021/004023 JP2021004023W WO2021176941A1 WO 2021176941 A1 WO2021176941 A1 WO 2021176941A1 JP 2021004023 W JP2021004023 W JP 2021004023W WO 2021176941 A1 WO2021176941 A1 WO 2021176941A1
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pha
twin
screw extruder
aqueous suspension
screw
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French (fr)
Japanese (ja)
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優 平野
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Kaneka Corp
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Kaneka Corp
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Priority to CN202180018180.4A priority Critical patent/CN115210299B/zh
Priority to US17/905,268 priority patent/US12528910B2/en
Priority to JP2022505059A priority patent/JPWO2021176941A1/ja
Publication of WO2021176941A1 publication Critical patent/WO2021176941A1/ja
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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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • 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
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2399/00—Characterised by the use of natural macromolecular compounds or of derivatives thereof not provided for in groups C08J2301/00 - C08J2307/00 or C08J2389/00 - C08J2397/00

Definitions

  • the present invention relates to a method for producing polyhydroxyalkanoate and its use.
  • PHA Polyhydroxyalkanoates
  • a step of separating and purifying PHA from the cells of microorganisms is required in order to use PHA as a plastic.
  • the step of separating and purifying PHA cells of PHA-containing microorganisms are crushed 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 (Patent Document 1).
  • an object of the present invention is to provide a manufacturing method capable of obtaining PHA by a simple operation as an alternative technique to spray drying.
  • one aspect of the present invention is to (a) prepare a PHA aqueous suspension having a pH of 7 or less, and (b) biaxially extrude the PHA aqueous suspension prepared in the above step (a).
  • the present invention relates to a method for producing polyhydroxyalkanoic acid, which comprises a step of aggregating PHA by heating in a machine at a set temperature of 80 to 300 ° C.
  • one aspect of the present invention relates to a polyhydroxyalkane aggregate containing 97% by weight or more of polyhydroxyalkanoic acid and having a volume median diameter of 300 ⁇ m or more.
  • PHA can be obtained by a simple operation.
  • the method for producing PHA according to one embodiment of the present invention includes (a) a step of preparing an aqueous suspension of PHA having a pH of 7 or less, and (b) the above.
  • the method comprises a step of heating the PHA aqueous suspension prepared in the step (a) at a set temperature of 80 to 300 ° C. in a twin-screw extruder to agglomerate the PHA.
  • the present inventor considered that there are the following problems when spray drying is performed in the production of PHA.
  • the spray drying operation requires enormous thermal energy because all the water in the aqueous suspension needs to be evaporated.
  • the spray dryer used for the spray drying operation tends to be huge, and there is a problem in that the equipment installation area becomes large.
  • the present inventor has the possibility of obtaining PHA aggregates more efficiently by using the method, and obtains useful PHA aggregates (for example, PHA aggregates having novel physical characteristics) that have never existed in the past. It also showed the possibility of being vulnerable.
  • this manufacturing method PHA can be obtained by a simple operation.
  • this manufacturing method is based on continuous production equipment, it is possible to save space in the equipment, and as a result, there is an advantage that the installation and movement of the manufacturing site can be facilitated. From this point of view, this manufacturing method can also be said to be a continuous manufacturing method of PHA. As mentioned above, this production method is extremely advantageous in the production of PHA.
  • the "double-screw extruder" used in the present manufacturing method shall also include a twin-screw kneader.
  • the configuration of this manufacturing method will be described in detail.
  • This manufacturing method is a method including the following steps (a) to (b) as essential steps.
  • Step (b): (b) The PHA aqueous suspension prepared in the above-mentioned step (a) is put into a twin-screw extruder. Step of agglomerating PHA by heating at a set temperature of 80 to 300 ° C. (step (a))
  • step (a) of this production method a PHA aqueous suspension having a pH of 7 or less is prepared.
  • PHA is present dispersed in an aqueous medium.
  • an aqueous suspension containing at least PHA may be abbreviated as "PHA aqueous suspension”.
  • PHA is a general term for polymers having hydroxyalkanoates as a monomer unit.
  • the hydroxyalkanoic acid constituting PHA is not particularly limited, and is, for example, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 3-hydroxypropionic acid, 3-hydroxypentanoic acid, 3-hydroxyhexanoic acid, 3-hydroxy. Examples thereof include heptanoic acid and 3-hydroxyoctanoic acid.
  • These polymers may be homopolymers or copolymers containing two or more kinds of monomer units.
  • PHA examples include poly (3-hydroxybutyrate) (P3HB), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH), and poly (3-hydroxybutyrate).
  • -Co-3-hydroxyvariate) P3HB3HV
  • poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P3HB4HB
  • poly (3-hydroxybutyrate-co-3-hydroxyoctanoate) P3HB3HO
  • Poly (3) -Hydroxybutyrate-co-3-hydroxyvariate-co-3-hydroxyhexanoate) P3HB3HV3HH
  • P3HB4HB are prefer
  • the melting point and the crystallinity can be changed, and as a result, the physical properties such as the Young rate and the heat resistance can be changed, and the physical properties between polypropylene and polyethylene can be changed.
  • a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid from the viewpoint of being able to be imparted and being a plastic that is industrially easy to produce and is physically useful as described above. Certain P3HB3HH is more preferred.
  • the composition ratio of the repeating unit of P3HB3HH is such that the composition ratio of 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit is 80/20 or more from the viewpoint of the balance between flexibility and strength. It is preferably 99/1 (mol / mol), more preferably 85/15 to 97/3 (mo1 / mo1).
  • the composition ratio of 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit is 99/1 (mol / mol) or less, sufficient flexibility is obtained, and when it is 80/20 (mol / mol) or more. If there is, sufficient hardness can be obtained.
  • the PHA aqueous suspension used as a starting material is not particularly limited, but for example, a culturing step of culturing a microorganism capable of producing PHA in cells, and after the culturing step, other than PHA. It can be obtained by a method including a purification step of decomposing and / or removing the substance of.
  • the present production method may include a step of obtaining a PHA aqueous suspension (for example, a step including the above-mentioned culture step and purification step) before the step (a).
  • the microorganism used in the step is not particularly limited as long as it is a microorganism capable of producing PHA in the cell.
  • microorganisms isolated from nature or microorganisms deposited in a strain depository for example, IFO, ATCC, etc.
  • mutants or transformants that can be prepared from them can be used.
  • Cupriavidus Alcaligenes, Ralstonia, Pseudomonas, Bacillus, Aeromonas, Azotobacter, Nocardia, Nocardia, Nocardia
  • bacteria of the genus include bacteria of the genus (Aeromonas).
  • microorganisms belonging to the genus Aeromonas, Alcaligenes, Ralstonia, or Cupriavidus are preferable.
  • the target PHA synthase gene and / or a variant thereof is 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 PHA synthase gene a PHA synthase gene derived from Aeromonas cavier is preferable. By culturing these microorganisms under appropriate conditions, it is possible to obtain microbial cells in which PHA is accumulated in the cells.
  • the method for culturing the microbial cells is not particularly limited. As the culture method, for example, the method described in Japanese Patent Application Laid-Open No. 05-93049 is used.
  • a purification step for decomposing and / or removing impurities other than PHA is usually performed. Can be carried out.
  • this purification step 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, the purification described in International Publication No. 2010/067543. The method is preferably applicable.
  • the amount of impurities remaining in the final product is roughly 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.
  • high-purity PHA is required for medical applications, it is preferable to reduce impurities 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, and for example, the above-mentioned known methods 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.
  • organic solvent compatible with water include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, acetonitrile, and pro.
  • Pionitrile or the like is preferable because it is easy to remove. Further, as the organic solvent compatible with the water, methanol, ethanol, 1-propanol, 2-propanol, butanol, acetone and the like are more preferable because they are easily available. Further, as the organic solvent compatible with the water, methanol, ethanol and acetone are particularly preferable.
  • the 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 40% by weight or more.
  • 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 pH of the aqueous PHA suspension is adjusted to 7 or less by the step (a) of the present production method.
  • the adjustment method is not particularly limited, and examples thereof include a method of adding an acid.
  • the acid is not particularly limited, and 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 7 from the viewpoint of reducing the coloring when the PHA is heated and melted and ensuring the stability of the molecular weight during heating and / or drying. It is less than or equal to, 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.
  • the pH of the aqueous PHA suspension may be prepared before being charged into the twin-screw extruder or after being charged into the twin-screw extruder. May be good.
  • the PHA aqueous suspension is first charged into the twin-screw extruder, and then the above-mentioned acid or the like is charged into the twin-screw extruder to carry the PHA aqueous suspension.
  • the pH of the turbid solution can be adjusted to 7 or less. It is preferable that the addition of the acid or the like is carried out before the PHA aqueous suspension is heated in the twin-screw extruder. As a result, it is possible to obtain PHA aggregates in which coloring during heating and melting in a twin-screw extruder is reduced, and reduction in molecular weight during heating and / or drying is suppressed.
  • the concentration of PHA in the aqueous suspension of PHA obtained in the step (a) of the present production method is economically advantageous from the viewpoint 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. Further, the upper limit of the concentration of PHA is preferably 70% by weight or less, more preferably 65% by weight or less, because it is a close-packed packing and sufficient fluidity may not be ensured.
  • the method for adjusting the concentration of PHA is not particularly limited, and examples thereof include methods such as adding an aqueous medium and removing a part of the aqueous medium (for example, by removing the supernatant after centrifugation). 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 to 70% by weight.
  • the PHA aqueous suspension prepared in the step (a) is heated at a set temperature of a twin-screw extruder of 80 to 300 ° C. to agglomerate the PHA. That is, in the step (b), the PHA aggregate can be obtained by putting the PHA aqueous suspension into the twin-screw extruder and moving the suspension in the twin-screw extruder while heating at a specific temperature. At this time, the pressurized steam may be directly charged into the twin-screw extruder to heat the PHA aqueous suspension to obtain PHA aggregates. At this time, PHA is bonded by heat fusion to obtain PHA aggregates.
  • the PHA aggregate obtained in this step is a lumpy PHA, which has a larger particle size and is easier to handle than the powdery PHA obtained by the spray drying step.
  • the set temperature of the twin-screw extruder in step (b) is PHA by heat fusion.
  • the temperature at which the agglomerates can be obtained is not particularly limited, but is, for example, 80 to 300 ° C., preferably 100 to 250 ° C., more preferably 120 to 240 ° C., and particularly preferably 140 to 140 ° C. It is 220 ° C.
  • the set temperature of the twin-screw extruder in the step (b) is 80 ° C. or higher, the water contained in the PHA aqueous suspension can be sufficiently volatilized.
  • the set temperature of the twin-screw extruder in the step (b) is 200 ° C. or lower, it is possible to avoid a decrease in molecular weight due to decomposition of PHA aggregates.
  • the heating method in the step (b) is not particularly limited, and can be carried out by using, for example, an electric heater, a steam heater, an oil heater, or the like, or by directly injecting pressurized steam into the twin-screw extruder. You can also do it. Further, the heating time is not particularly limited and can be appropriately set by those skilled in the art.
  • the number of rotations of the screw of the twin-screw extruder (also referred to as "shaft rotation speed”) is not particularly limited, but is, for example, 20 to 1000 rpm, preferably 25 to 800 rpm, and more. Preferably, it is 28 to 700 rpm.
  • the rotation speed of the screw of the twin-screw extruder is 20 rpm or more, the shaft adhesion of PHA can be suppressed.
  • the rotation speed of the screw of the twin-screw extruder is 1000 rpm or less, PHA can be effectively aggregated.
  • a part of the screw of the twin-screw extruder may be a screw having a reverse feed action (hereinafter, may be referred to as a "return screw").
  • a return screw When the twin-screw extruder is provided with a return screw, pressure is applied at the return screw portion. As a result, heat is uniformly transferred not only to the surface of the PHA aqueous suspension but also to the inside, and heat fusion can be performed uniformly without evaporating the water content.
  • the number of return screws is not particularly limited and may be one or a plurality (for example, two, three, four, five).
  • the pressure in the twin-screw extruder in step (b) is not particularly limited as long as it is at a temperature at which PHA aggregates can be obtained by heat fusion, but for example, 0.01 to 0.5 Mpa. It is preferably 0.05 to 0.5 Mpa, and more preferably 0.08 to 0.5 Mpa.
  • the pressure in the twin-screw extruder in the step (b) when the twin-screw extruder is provided with a return screw is, for example, 0.1 to 0.5 Mpa, preferably 0.2 to 0.5 Mpa. More preferably, it is 0.25 to 0.5 Mpa.
  • step (b) in order to obtain a desired PHA aggregate, in step (b), the set temperature of the twin-screw extruder, the rotation speed of the screw of the twin-screw extruder, the return screw, and the twin-screw extruder.
  • the pressure inside can be combined as appropriate.
  • the twin-screw extruder used in this production method is not particularly limited as long as PHA aggregates can be obtained from the PHA aqueous suspension, but the set temperature, screw rotation speed, pressure and the like can be desired.
  • a twin-screw extruder that can be adjusted to a range is preferable.
  • FIGS. 1 to 5 show schematically a typical twin-screw extruder that can be used in this manufacturing method.
  • the commercially available twin-screw extruder used in this manufacturing method is not particularly limited, but for example, the EA-20 manufactured by Suehiro EPM, the S2KRC kneader manufactured by Kurimoto Steel Works, and the Japan Steel Works Co., Ltd. used in the examples. TEX60 ⁇ and the like.
  • PHA aggregates can be obtained by this production method.
  • the fact that the PHA aggregate was obtained can be indicated by using the value represented by the following formula (1) as an index: Volume median diameter of PHA aggregates obtained in step (b) / Volume median diameter of PHA primary particles ...
  • PHA primary particle means the particle of PHA contained in the polyhydroxyalkanoic acid aqueous suspension prepared in step (a).
  • the "volume median diameter of PHA aggregates” can also be referred to as "average particle size of PHA aggregates”.
  • the "volume median diameter of PHA primary particles” can also be referred to as "PHA primary particle diameter”.
  • the value represented by the above formula (1) is, for example, 50 to 20000, preferably 100 to 15000, and more preferably 150 to 10000.
  • volume median diameter of PHA aggregate is measured by the following method. That is, To 20 ml of ion-exchanged water, 0.05 g of sodium dodecyl sulfate as a surfactant is added as a dispersant to obtain an aqueous surfactant solution. Then, 0.2 g of the resin particle group to be measured is added to the surfactant aqueous solution, and the resin particle group is dispersed in the surfactant aqueous solution to obtain a dispersion liquid for measurement. The prepared dispersion liquid is introduced into a laser diffraction / scattering type particle size distribution measuring device LA-950 manufactured by HORIBA, and measurement is performed.
  • LA-950 laser diffraction / scattering type particle size distribution measuring device
  • volume median diameter of PHA primary particles is measured using a laser diffraction / scattering type particle size distribution measuring device LA-950 manufactured by HORIBA.
  • the twin-screw extruder used in the first embodiment adjusts the temperature in the screw 2 for transferring the charged sample, the extruder power source 4 for supplying the power for rotating the screw 2, and the twin-screw extruder. It is provided with a heating heater 3 to be used, and an extrusion unit (discharging unit) 5 from which the transferred sample is extruded.
  • the set temperature of the heater 3 can be, for example, 140 to 150 ° C.
  • the PHA aqueous suspension which is a sample, is charged into the twin-screw extruder from the PHA aqueous suspension charging unit 10.
  • the pH of the PHA aqueous suspension before being charged into the twin-screw extruder is adjusted to 7 or less. That is, the PHA aqueous suspension having a pH of 7 or less is charged into the twin-screw extruder.
  • the amount of the PHA aqueous suspension charged into the twin-screw extruder is adjusted by the valve 8.
  • the PHA aqueous suspension charged into the extruder internal region 1 is transferred toward the extrusion portion (discharge portion) 5 by the screw 2.
  • the PHA in the PHA aqueous suspension is combined by heat fusion and discharged as a PHA aggregate from the extrusion portion (discharge portion) 5.
  • the PHA aggregate can be obtained from the PHA aqueous suspension most easily.
  • the twin-screw extruder used in the second embodiment is the same as the twin-screw extruder used in the first embodiment.
  • the PHA aqueous suspension which is a sample, is charged into the twin-screw extruder from the PHA aqueous suspension charging unit 10.
  • the pH of the PHA aqueous suspension before being charged into the twin-screw extruder is not adjusted to 7 or less. That is, a PHA aqueous suspension having a pH greater than 7 is charged into the twin-screw extruder.
  • the pH of the PHA aqueous suspension charged into the extruder internal region 1 is adjusted to 7 or less by adding an acid from the acid charging section 11. The amount of acid added is regulated by the valve 8.
  • the PHA aqueous suspension prepared to have a pH of 7 or less is transferred toward the extrusion portion (discharge portion) 5 by the screw 2 as in the first embodiment, and a PHA aggregate is obtained.
  • the pH of the aqueous PHA suspension and the drying of the aqueous PHA suspension can be collectively performed in the extruder internal region 1.
  • the twin-screw extruder used in the third embodiment includes a pressure reducing unit 6 for reducing the pressure in the twin-screw extruder in the twin-screw extruder used in the first embodiment.
  • the decompression unit 6 is connected to the vacuum pump 7. By operating the vacuum pump 7, the air in the twin-screw extruder is discharged through the decompression unit 6, and the pressure in the twin-screw extruder is reduced. Further, the decompression unit 6 may be opened to the atmosphere. By opening to the atmosphere, the water in the PHA aqueous suspension that evaporates in the twin-screw extruder can be discharged to the outside of the apparatus, and the evaporation efficiency can be improved.
  • the vacuum pump 7 By using the vacuum pump 7 to reduce the pressure in the twin-screw extruder, the evaporation of water in the PHA aqueous suspension can be promoted. Further, since the PHA aqueous suspension can be dried even if the temperature in the twin-screw extruder is lowered, decomposition of PHA (decrease in molecular weight) can be prevented.
  • a PHA aqueous suspension whose pH is not adjusted to 7 or less (pH is greater than 7) is charged into a twin-screw extruder, and the pH of the PHA aqueous suspension is adjusted in the twin-screw extruder. It can be prepared to 7 or less.
  • the twin-screw extruder used in the fourth embodiment is the twin-screw extruder used in the third embodiment, in which the heater 3 is divided into a plurality of regions having different temperature zones. Specifically, in the fourth embodiment, the heater 3 is divided into a high temperature portion 3a, a medium temperature portion 3b, and a low temperature portion 3c, which are in different temperature zones. The temperatures of the high temperature portion 3a, the medium temperature portion 3b, and the low temperature portion 3c are shown as Ta , T b, and T c, respectively.
  • T a , T b and T c have a relationship of, for example, Ta > T b > T c
  • the PHA aqueous suspension charged into the twin-screw extruder first evaporates water in the region of the high temperature portion 3 a. Then, the remaining water evaporates in the regions of the medium temperature portion 3b and the low temperature portion 3c.
  • T a, T b and T c is, for example, 0.99 ° C., may be 120 ° C. and 80 ° C..
  • the PHA is decomposed by gradually lowering the temperature in the twin-screw extruder from the region where the PHA aqueous suspension is charged toward the extrusion portion (discharge portion) 5. (Reduction in molecular weight) can be prevented.
  • the number of different temperature zones in the heater 3 can be set as appropriate. Further, the temperature in each temperature zone can be set as appropriate.
  • a PHA aqueous suspension whose pH is not adjusted to 7 or less (pH is greater than 7) is charged into a twin-screw extruder, and the pH of the PHA aqueous suspension is adjusted in the twin-screw extruder. It can be prepared to 7 or less.
  • the twin-screw extruder used in the fifth embodiment is the twin-screw extruder used in the first embodiment, and the screw 2 of the twin-screw extruder is provided with a screw (return screw) 9 having a reverse feed action. It is a screw.
  • the screw (return screw) 9 having a reverse feed action has a function of pushing back the PHA aqueous suspension in the direction opposite to the direction in which the PHA aqueous suspension is transferred.
  • the PHA aqueous suspension transferred from the extruder internal region 1 by the screw 2 is pressurized in the region provided with the screw (return screw) 9 having a reverse feed action.
  • heat is uniformly transferred not only to the surface of the PHA aqueous suspension but also to the inside, and heat fusion can be performed uniformly without evaporating the water content.
  • a PHA aqueous suspension whose pH is not adjusted to 7 or less (pH is greater than 7) is charged into a twin-screw extruder, and the pH of the PHA aqueous suspension is adjusted in the twin-screw extruder. It can be prepared to 7 or less.
  • the twin-screw extruder used in the sixth embodiment is the twin-screw extruder used in the first embodiment and includes a pressurized steam inlet 12.
  • a pressurized steam inlet 12 By injecting pressurized steam from the pressurized steam inlet 12, the temperature of the PHA aqueous suspension is rapidly raised, and heat fusion can be performed uniformly without evaporating water.
  • a screw (return screw) 9 having a reverse feed action is provided as a part of the screw 2 of the twin-screw extruder according to the fifth embodiment.
  • a PHA aqueous suspension whose pH is not adjusted to 7 or less (pH is greater than 7) is charged into a twin-screw extruder, and the pH of the PHA aqueous suspension is adjusted in the twin-screw extruder. It can be prepared to 7 or less.
  • a drying step may be added.
  • the drying method is not particularly limited, but for example, a band dryer, a conveyor dryer, a rotary dryer, or the like can be used.
  • the PHA aggregate according to one embodiment of the present invention contains 97% by weight or more of PHA and has a volume median diameter of 300 ⁇ m or more, excluding the amount of water. be. Since the present PHA aggregate is produced by the present production method, it has an advantage that it can be obtained by a simple operation. In other words, "containing 97% by weight or more of PHA excluding the amount of water” means PHA obtained by removing the amount of water from all the components (PHA, water, and impurities) contained in the present PHA aggregate. And it means that it contains 97% by weight or more of PHA with respect to the total amount of impurities.
  • the PHA aggregates herein also include PHA granules.
  • the present PHA aggregate can be produced by the above-mentioned characteristic production method, a fixing agent or the like is not required as compared with pellets containing PHA powder. Therefore, PHA is contained in the PHA aggregate at a high content.
  • This PHA agglomerate can also be paraphrased as a PHA granulator.
  • the PHA content in the PHA aggregate may be 97% by weight or more and is not particularly limited, but from the viewpoint of the influence on processability, 98% by weight or more is preferable, 99% by weight or more is more preferable, and 99% by weight or more. More preferably, it is 5.5% by weight or more.
  • the upper limit of the PHA content in the PHA aggregate is not particularly limited, but is, for example, 100% by weight or less.
  • the PHA content in the PHA aggregates is measured by high performance liquid chromatography.
  • the present PHA aggregate can be produced by the above-mentioned characteristic production method, it is possible to obtain a PHA aggregate having a larger size than a pellet containing PHA powder.
  • the volume median diameter (size) of the PHA aggregate may be 300 ⁇ m or more and is not particularly limited, but from the viewpoint of fluidity, 350 ⁇ m or more is preferable, 380 ⁇ m or more is more preferable, and 400 ⁇ m or more is further preferable.
  • the upper limit of the volume median diameter of the PHA aggregate is not particularly limited, but is, for example, 5 mm or less.
  • the volume median diameter of the PHA aggregate is measured by the method described above.
  • the shape of the PHA aggregate is not particularly limited, and may be various shapes such as granular, spherical, indefinite, rectangular (polygonal), and columnar.
  • the PHA aggregate 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 agglomerate can be used for various purposes such as paper, film, sheet, tube, plate, rod, container (for example, bottle container, etc.), bag, parts, and the like.
  • one embodiment of the present invention is as follows. ⁇ 1> (a) A step of preparing a PHA aqueous suspension having a pH of 7 or less, and (b) a PHA aqueous suspension prepared in the step (a) at a set temperature of 80 in a twin-screw extruder. A step of aggregating PHA by heating at ⁇ 300 ° C. A method for producing PHA, including. ⁇ 2> The polyhydroxyalkano according to ⁇ 1>, wherein the heating method in the step (b) is a method using a twin-screw extruder heater and / or a method of directly feeding pressurized steam into the twin-screw extruder. Method of producing acid.
  • ⁇ 3> The method for producing PHA according to ⁇ 1> or ⁇ 2>, wherein the value represented by the following formula (1) is 50 to 20000. Volume median diameter of PHA aggregates obtained in step (b) / Volume median diameter of PHA primary particles ... (1)
  • ⁇ 4> The method for producing polyhydroxyalkanoic acid according to any one of ⁇ 1> to ⁇ 3>, wherein the PHA concentration in the aqueous PHA suspension is 30 to 70% by weight in the step (a).
  • ⁇ 5> The method for producing PHA according to any one of ⁇ 1> to ⁇ 4>, wherein the rotation speed of the screw of the twin-screw extruder is 30 to 1000 rpm.
  • ⁇ 6> The method for producing PHA according to any one of ⁇ 1> to ⁇ 5>, wherein the pressure in the twin-screw extruder is 0.01 to 0.5 Mpa.
  • ⁇ 7> The method for producing PHA according to any one of ⁇ 1> to ⁇ 6>, wherein a part of the screw of the twin-screw extruder is a screw having a reverse feed action.
  • ⁇ 8> A polyhydroxyalkane aggregate containing 97% by weight or more of polyhydroxyalkanoic acid and having a volume median diameter of 300 ⁇ m or more.
  • Example 1 (Preparation of bacterial cell culture solution)
  • the Ralstonia utrofa KNK-005 strain described in paragraph [0049] of WO 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 cell culture solution obtained above was heated and stirred at an internal temperature of 60 to 80 ° C. for 20 minutes to be sterilized.
  • the volume median diameter of the PHA particles (PHA primary particles) in the PHA aqueous suspension was measured and found to be 2.5 ⁇ m.
  • Example 2 PHA aggregates were obtained in the same manner as in Example 1 except that the temperature of the heater of the twin-screw extruder was set to 140 ° C.
  • the volume median diameter of the obtained PHA aggregate was 836 ⁇ m.
  • the volume median diameter of the PHA aggregate / the volume median diameter of the PHA primary particles was 334.4.
  • the PHA content in the PHA aggregate was 98.9% by weight.
  • Example 4 PHA aggregates were obtained in the same manner as in Example 3 except that the slurry charging rate was 5.0 kg / h.
  • the volume median diameter of the obtained PHA aggregate was 611 ⁇ m.
  • the volume median diameter of the PHA aggregate / the volume median diameter of the PHA primary particles was 244.4.
  • the PHA content in the PHA aggregate was 98.9% by weight.
  • Example 5 PHA aggregates were obtained in the same manner as in Example 4 except that the shaft rotation speed was set to 100 rpm.
  • the volume median diameter of the obtained PHA aggregate was 444 ⁇ m.
  • the volume median diameter of the PHA aggregate / the volume median diameter of the PHA primary particles was 177.6.
  • the PHA content in the PHA aggregate was 98.9% by weight.
  • Example 6 PHA aggregates were obtained in the same manner as in Example 3 except that the slurry charging speed was 10.0 kg / h and the heater temperature was 165 ° C.
  • the volume median diameter of the obtained PHA aggregate was 1164 ⁇ m.
  • the volume median diameter of the PHA aggregate / the volume median diameter of the PHA primary particles was 465.6.
  • the PHA content in the PHA aggregate was 98.9% by weight.
  • Example 1 The same method as in Example 1 was carried out except that the temperature of the heater of the twin-screw extruder was set to 50 ° C. As a result, the PHA aqueous suspension was discharged from the discharge section of the twin-screw extruder, and no PHA aggregate was obtained.
  • this production method can produce PHA by a simple operation, it can be advantageously used in the production of PHA.
  • the PHA aggregates and 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. ..
  • Extruder internal area 2 Screw 3 Heater 3a High temperature part 3b Medium temperature part 3c Low temperature part 4 Extruder dynamic source part 5 Extruder part (extrusion part) 6 Decompression unit 7 Vacuum pump 8 Valve 9 Screw with reverse feed action (return screw) 10 PHA Aqueous Suspension Charger 11 Acid Charger 12 Pressurized Steam Charger

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024029514A1 (ja) * 2022-08-05 2024-02-08 株式会社カネカ ポリヒドロキシアルカノエートの製造方法およびその利用
WO2025134498A1 (ja) * 2023-12-18 2025-06-26 三菱瓦斯化学株式会社 ポリヒドロキシアルカン酸凝集体の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001114901A (ja) * 1999-10-22 2001-04-24 Technology Resources Incorporated:Kk 球状複合粉体の製造方法
JP2002240033A (ja) * 2001-02-22 2002-08-28 Teijin Chem Ltd ポリカーボネート樹脂粉粒体の製造方法
JP3773526B2 (ja) * 1992-07-24 2006-05-10 メタボリックス・インコーポレーテッド ポリマーの粒度を高める方法
WO2012029448A1 (ja) * 2010-09-03 2012-03-08 株式会社クレハ 顆粒状脂肪族ポリエステル粒子、及び、その製造方法
JP2019097518A (ja) * 2017-12-06 2019-06-24 株式会社カネカ ポリヒドロキシアルカノエート分散液の製造方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI970679A7 (fi) 1994-08-18 1997-04-16 Monsanto Co Hydroksialkaanihapoista muodostettujen polymeerien valmistus
EP1698665B1 (en) * 2000-12-21 2008-06-04 Meredian, Inc. Method for making biodegradable polyhydroxyalkanoate copolymers having improved crystallization properties
JP4520843B2 (ja) 2004-12-15 2010-08-11 株式会社カネカ 生分解性フィルムの製造方法
US20110256398A1 (en) * 2008-04-17 2011-10-20 Yelena Kann Production Of Non-Woven Materials From Polyhydroxyalkanoate
WO2010067543A1 (ja) 2008-12-09 2010-06-17 株式会社カネカ ポリ－３－ヒドロキシアルカン酸の製造方法およびその凝集体
US10433543B2 (en) * 2014-10-15 2019-10-08 Terraverdae Bioworks Inc. Bioactive biopolymer films and coatings
CN107075134B (zh) * 2014-11-14 2021-03-09 赢创运营有限公司 制备微粒形式的生物可再吸收聚酯的方法
US11814500B2 (en) * 2015-03-31 2023-11-14 Algix, Llc Algae-blended thermoplastic compositions
CN109843985B (zh) 2016-10-13 2022-06-07 株式会社钟化 聚羟基链烷酸酯的制造方法
KR20210121200A (ko) * 2019-01-30 2021-10-07 바스프 에스이 전분 블렌드의 제조 방법
EP4342669A4 (en) * 2021-05-17 2025-04-16 Kaneka Corporation LAMINATE, PACKAGING MATERIAL AND CONTAINER
EP4460540A1 (en) * 2022-02-16 2024-11-13 IMI Fabi S.p.A. Talc particulate with a particularly low migration factor for the use as fillers in food contact materials (fcms)

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3773526B2 (ja) * 1992-07-24 2006-05-10 メタボリックス・インコーポレーテッド ポリマーの粒度を高める方法
JP2001114901A (ja) * 1999-10-22 2001-04-24 Technology Resources Incorporated:Kk 球状複合粉体の製造方法
JP2002240033A (ja) * 2001-02-22 2002-08-28 Teijin Chem Ltd ポリカーボネート樹脂粉粒体の製造方法
WO2012029448A1 (ja) * 2010-09-03 2012-03-08 株式会社クレハ 顆粒状脂肪族ポリエステル粒子、及び、その製造方法
JP2019097518A (ja) * 2017-12-06 2019-06-24 株式会社カネカ ポリヒドロキシアルカノエート分散液の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024029514A1 (ja) * 2022-08-05 2024-02-08 株式会社カネカ ポリヒドロキシアルカノエートの製造方法およびその利用
WO2025134498A1 (ja) * 2023-12-18 2025-06-26 三菱瓦斯化学株式会社 ポリヒドロキシアルカン酸凝集体の製造方法

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