WO2024029491A1 - ３－ヒドロキシ酪酸からなるコポリエステル及びその製造方法 - Google Patents

３－ヒドロキシ酪酸からなるコポリエステル及びその製造方法 Download PDF

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WO2024029491A1
WO2024029491A1 PCT/JP2023/027951 JP2023027951W WO2024029491A1 WO 2024029491 A1 WO2024029491 A1 WO 2024029491A1 JP 2023027951 W JP2023027951 W JP 2023027951W WO 2024029491 A1 WO2024029491 A1 WO 2024029491A1
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acid
copolyester
hydroxybutyric acid
derived
mol
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English (en)
French (fr)
Japanese (ja)
Inventor
翔 稲垣
啓 高野
英知 甲斐
敦好 中山
典起 川崎
尚子 山野
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DIC Corp
National Institute of Advanced Industrial Science and Technology AIST
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DIC Corp
National Institute of Advanced Industrial Science and Technology AIST
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2024536081A priority Critical patent/JP7620957B2/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
    • C08G63/02—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
    • 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
    • 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

Definitions

  • the present invention relates to a copolyester consisting of 3-hydroxybutyric acid and a method for producing the same.
  • Patent Document 1 describes a copolyester of 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and lactic acid, wherein the copolyester contains 3-hydroxybutyric acid units in an amount of 10 to 25 mol% based on the total structural units.
  • a copolymer resin composition includes a biodegradable copolyester content.
  • Non-Patent Document 1 describes a copolyester consisting of 3-hydroxybutyric acid and lactic acid, in which the content of 3-hydroxybutyric acid units is 50 to 78% of the total constituent units, and the average chain of 3-hydroxybutyric acid units is 50 to 78%.
  • Biodegradable copolyesters having a length of 2.7 to 22.3 are disclosed.
  • Patent Document 1 and Non-Patent Document 1 contain information on the content of 3-hydroxybutyric acid units relative to all constituent units (hereinafter also referred to as “3HB content”) and the average chain length of 3-hydroxybutyric acid (hereinafter referred to as “3HB content”). , sometimes referred to as “3HB chain length”) on biodegradability is not clear, and it was not possible to predict whether biodegradability would occur especially when the 3HB ratio was 50% or less.
  • the present invention was made to solve the above-mentioned problems, and provides a copolyester (hereinafter also referred to as "3HB copolyester”) consisting of 3-hydroxybutyric acid that exhibits high biodegradability at a specific 3HB ratio and 3HB chain length.
  • the purpose of the present invention is to provide a method for manufacturing the same.
  • the content of the present disclosure includes the following embodiments [1] to [8].
  • the copolyester has a structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) and a structural unit (HA-U) derived from hydroxyalkanoic acid (HA),
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) is 1 to 40 mol% with respect to 100 mol of the total structural units of the copolyester
  • a copolyester characterized in that the average chain length of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) in the copolyester is 2 to 20.
  • a method for producing a copolyester comprising the steps of: [7] A resin composition containing the copolyester according to any one of [1] to [5]. [8] A sheet or film made of the resin composition according to [7].
  • 1 is a 1 H-NMR spectrum of the copolyester of Example 1 of the present invention.
  • 1 is a 13 C-NMR spectrum of the copolyester of Example 1 of the present invention.
  • ⁇ means a value greater than or equal to the value before the description " ⁇ ” and less than or equal to the value after the description " ⁇ ".
  • the copolyester of one embodiment of the present invention is a copolyester of 3-hydroxybutyric acid (3HB) and hydroxyalkanoic acid (HA) (sometimes referred to as HB-HA copolyester). be.
  • the copolyester of the present embodiment has a structural unit (3HB-U) derived from the 3-hydroxybutyric acid (3HB) and a structural unit (HA-U) derived from the hydroxyalkanoic acid (HA).
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) is 1 to 40 mol% with respect to 100 mol of all structural units of the copolyester.
  • the average chain length of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) in the copolyester is 2 to 20.
  • the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) means one residue of 3-hydroxybutyric acid in the copolymer, and specifically, the structural unit derived from the hydrogen atom in the hydroxyl group of 3-hydroxybutyric acid and It means a structure excluding the hydroxyl residue in the carboxyl group.
  • the structural unit (HA-U) derived from hydroxyalkanoic acid (HA) means one residue of hydroxyalkanoic acid in the copolymer, and specifically, the structural unit derived from the hydrogen atom in the hydroxy group and the carboxyl group of the hydroxyalkanoic acid. means the structure excluding the hydroxyl residue.
  • the total number of constituent units of the copolyester means the total number of moles of constituent units derived from all monomers constituting the copolyester.
  • the copolyester of the present embodiment has a structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) and a structural unit (HA-U) derived from hydroxyalkanoic acid (HA), and When the copolyester does not contain any other structural units, all the structural units of the copolyester are the structural unit derived from 3-hydroxybutyric acid (3HB) (3HB-U) and the structural unit derived from hydroxyalkanoic acid (HA) (HA- U) is the total number of moles.
  • the content (mol%) of structural units derived from 3-hydroxybutyric acid (3HB) (3HB-U) is the content (mol%) of structural units derived from 3-hydroxybutyric acid (3HB) relative to the total number of moles of structural units derived from all monomers constituting the copolyester. It is the percentage of the number of moles of the structural unit (3HB-U) derived from 3HB).
  • the chain structure of the structural unit derived from 3-hydroxybutyric acid (3HB-U) means a structure in which one residue of 3-hydroxybutyric acid is linked with an ester bond, specifically, the hydroxy group of 3-hydroxybutyric acid It means a structure in which the hydrogen atom inside and the structure excluding the hydroxyl residue in the carboxyl group are continuously ester-bonded.
  • the average chain length of the structural units derived from 3-hydroxybutyric acid (3HB-U) is the average value of the number of consecutive structural units derived from 3-hydroxybutyric acid in a sequence of one polyester molecule. The evaluation method will be explained in Examples below.
  • the copolyester of the present embodiment is preferably a reaction product of the poly(3-hydroxybutyric acid) (PHB) and the hydroxyalkanoic acid (HA) or the polyester (PHA) of the hydroxyalkanoic acid (HA).
  • PB poly(3-hydroxybutyric acid)
  • HA hydroxyalkanoic acid
  • PHA polyester of the hydroxyalkanoic acid
  • Polyester of 3-hydroxybutyric acid (3HB) (PHB) is a polyester in which constituent units derived from 3-hydroxybutyric acid are consecutively ester bonded, and specifically, the polyester is a polyester in which constituent units derived from 3-hydroxybutyric acid are bonded with ester bonds.
  • the structure excluding the hydroxyl residue in the carboxyl group is a polyester with continuous ester bonds.
  • Polyester (PHA) of hydroxyalkanoic acid (HA) is a polyester in which constituent units derived from hydroxyalkanoic acid (HA) are continuously ester-bonded, and specifically, the polyester in the hydroxyl group of hydroxyalkanoic acid (HA) is It is a polyester in which the structure excluding hydrogen atoms and hydroxyl residues in carboxyl groups is continuously linked with ester bonds.
  • copolyester of this embodiment include the following formulas (1) to (3).
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) according to the present embodiment is 1 to 40 mol%, with respect to 100 mol of all structural units of the copolyester of the present embodiment, and 2 It is preferably from 30 mol% to 30 mol%, more preferably from 3 to 25 mol%, even more preferably from 4 to 20 mol%. Any combination of these upper and lower limits may be used. If the content of the structural unit (3HB-U) is less than 1 mol%, the biodegradability of the copolyester decreases. When the content of the structural unit (3HB-U) exceeds 40 mol%, acidic decomposition products of 3-hydroxybutyric acid are likely to be generated, causing problems such as generation of an unpleasant odor and easy hydrolysis.
  • the average chain length of the structural unit derived from 3-hydroxybutyric acid (3HB-U) in the copolyester of the present embodiment is 2 to 20, preferably 3 to 15, and more preferably 4 to 10. , more preferably 5 to 8. Any combination of these upper and lower limits may be used.
  • the average chain length of the structural unit (3HB-U) is less than 2, not only the biodegradability of the copolyester but also the mechanical properties and melting point are reduced.
  • the average chain length of the structural units (3HB-U) exceeds 20, the biodegradability of the copolyester decreases.
  • the content of the 3-hydroxybutyric acid (3HB)-derived structural unit (3HB-U) according to the present embodiment is 4 to 20 mol% with respect to 100 mol of all structural units of the copolyester of the present embodiment, and
  • the average chain length of the structural unit (3HB-U) derived from 3-hydroxybutyric acid in the copolyester of the present embodiment is 5 to 8, high biodegradability, mechanical properties, and melting point can be achieved, and 3-hydroxybutyric acid It is particularly preferable because it can also suppress the decomposition of .
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) according to the present embodiment can be measured by the 1 H-NMR spectrum of the copolyester of the present embodiment, and in detail, the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) can be measured by the 1 H-NMR spectrum of the copolyester of the present embodiment. It can be measured by the method described in .
  • the content of the structural unit (3HB-U) is determined by the amount of 3-hydroxybutyric acid (3HB) in the raw material for producing the copolyester (or the raw material for the intermediate product) in the copolyester production method of the present embodiment described below. It can be prepared with
  • the average chain length of the 3-hydroxybutyric acid-derived structural unit (3HB-U) in the copolyester of this embodiment can be measured by 1 H-NMR and 13 C-NMR spectra of the copolyester of this embodiment, and can be determined in detail. can be measured by the method described in the Examples below.
  • the average chain length of the structural unit (3HB-U) can be determined by, for example, the esterification reaction between 3-hydroxybutyric acids, the esterification between 3-hydroxybutyric acid and hydroxyalkanoic acid in the method for producing a copolyester of the present embodiment described below. It can be adjusted by controlling the reaction (for example, block polymerization, etc.).
  • Examples include a method of controlling the order in which each raw material is added, a method of adjusting the speed of each reaction, and the like. For example, a method in which 3-hydroxybutyric acid (3HB) oligomer or polyester (PHB) is first obtained and then hydroxyalkanoic acid (HA) is charged; Examples include a method of obtaining a polyester (PHA) of hydroxyalkanoic acid (HA) and then reacting the obtained polyester (PHB) with the polyester (PHA).
  • the 3-hydroxybutyric acid of the present invention can be used in any of racemic form, (R) form, and (S) form. It is particularly preferable to use the (R) isomer because it can exhibit high biodegradability, mechanical properties, and melting point.
  • HA hydroxyalkanoic acid
  • HA-U hydroxyalkanoic acid
  • examples of the hydroxyalkanoic acid (HA) according to the present embodiment include glycolic acid, 2-hydroxypropanoic acid (lactic acid), 3-hydroxypropanoic acid, 2-hydroxybutanoic acid (2-hydroxybutyric acid), 4-hydroxybutane Acid, 3-hydroxy-3-methyl-butanoic acid, 2-hydroxypentanoic acid (2-hydroxyvaleric acid), 3-hydroxypentanoic acid, 5-hydroxypentanoic acid, 2-hydroxy-2-methyl-pentanoic acid, 3 -Hydroxyhexanoic acid, 6-hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 3-hydroxyheptanoic acid, 7-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 8-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 9-hydroxy Hydroxy C 2-15 alkanoic acids which may have a C 1-6 alky
  • hydroxyalkanoic acid may be a corresponding lactone.
  • lactones include those having a diC 1-12 alkyl group, such as ⁇ -propiolactone, ⁇ -dimethylpropiolactone, ⁇ -butyrolactone, ⁇ -dimethylbutyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone. Examples include good C 3-15 lactones.
  • hydroxyalkanoic acids and lactones can be used alone or in combination of two or more.
  • hydroxyalkanoic acids from the viewpoint of biodegradability, 3-hydroxypropanoic acid, 4-hydroxybutanoic acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 6-hydroxyhexanoic acid, and 3-hydroxyheptanoic acid , 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid (hydroxyC 3-10 alkanoic acid units other than 3-hydroxybutyric acid) or the corresponding lactones are preferred.
  • the hydroxyalkanoic acid (HA) according to this embodiment is particularly preferably 2-hydroxypropanoic acid (lactic acid). That is, the structure (HA-U) derived from hydroxyalkanoic acid (HA) according to the present embodiment is particularly preferably a structure derived from 2-hydroxypropanoic acid (lactic acid).
  • other structural units include 3-hydroxybutyric acid. and units derived from hydroxycarboxylic acids (HCA) other than hydroxyalkanoic acids (HA) (HCA-U) (other hydroxycarboxylic acid units including lactone units may be included).
  • the copolyester of this embodiment contains other structural units in addition to the above-mentioned 3HB-derived structural unit (3HB-U) and hydroxyalkanoic acid (HA)-derived structural unit (HA-U), this embodiment
  • the molar content of other structural units is preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less with respect to 100 mol of all structural units of the copolyester. It is even more preferable.
  • the molar content of other structural units may be 5 mol % or more with respect to 100 mol of all structural units of the copolyester of this embodiment.
  • hydroxycarboxylic acid units examples include units of hydroxycycloalkanecarboxylic acid (hydroxycyclohexanecarboxylic acid, etc.), hydroxybenzoic acid (hydroxyarenecarboxylic acid, etc.), and the like. These hydroxycarboxylic acid units can be used alone or in combination of two or more.
  • the copolyester of the present embodiment is a copolyester of 3-hydroxybutyric acid (3HB) and hydroxyalkanoic acid (HA), in which the poly(3-hydroxybutyric acid) (PHB) and the hydroxyalkanoic acid (HA) are copolyesters. ) or a reaction product of the hydroxyalkanoic acid (HA) with a polyester (PHA).
  • the content of the structural unit (HB-U) derived from 3-hydroxybutyric acid (3HB) is 1 to 40 mol% with respect to 100 mol of the total structural units of the copolyester.
  • the average chain length of the 3-hydroxybutyric acid units in the copolyester is preferably 2 to 20.
  • the content of the structural unit (HB-U) derived from 3-hydroxybutyric acid (3HB) is 2 to 30 mol% with respect to 100 mol of all structural units of the copolyester, and It is more preferable that the average chain length of the 3-hydroxybutyric acid units in is 3 to 15.
  • the content of the structural unit (HB-U) derived from 3-hydroxybutyric acid (3HB) is 4 to 20 mol% with respect to 100 mol of all structural units of the copolyester, and It is more preferable that the average chain length of the 3-hydroxybutyric acid units in is 5 to 8.
  • the lower limit of the weight average molecular weight (Mw) of the copolyester of the present embodiment may be 5,000 or more, 6,000 or more, or 7,000 or more in terms of polystyrene when measured by gel permeation chromatography (GPC).
  • the upper limit may be 8,000 or more, 10,000 or more, the upper limit may be 1,000,000 or less, 500,000 or less, 100,000 or less, 50,000 or less, 30 ,000 or less. Any combination of these upper and lower limits may be used.
  • the number average molecular weight (Mn) of the copolyester is 1,000,000 or more, molding becomes difficult.
  • the number average molecular weight (Mn) of the copolyester is 5,000 or less, sufficient mechanical properties etc. are not exhibited.
  • the copolyester of this embodiment can improve biodegradability, so it can achieve both biodegradability and mechanical properties to a high degree.
  • the above-mentioned preferable structural range of the copolyester of this embodiment can be selected as appropriate depending on the use and the like.
  • the degree of biodegradation can be easily adjusted by adjusting the content of structural units derived from 3-hydroxybutyric acid.
  • the poly(3-hydroxybutyric acid) (PHB) according to the present embodiment is preferably poly(3-hydroxybutyric acid) obtained by subjecting 3-hydroxybutyric acids (3HB) to an esterification reaction.
  • Poly(3-hydroxybutyric acid) (PHB) according to the present embodiment includes a poly(3-hydroxybutyric acid) structure obtained by subjecting 3-hydroxybutyric acids (3HB) to an esterification reaction.
  • the method for producing poly(3-hydroxybutyric acid) is not particularly limited, and includes, for example, a method similar to the method for producing polylactic acid described in Non-Patent Document A below.
  • Non-patent Document A Shinji Yamada, Aknori Takasu, Sadatsugu Takayama, Kazuhiko Kawamura, Microwave-assisted solution polycondensation of L-lactic acid using a Dean-Stark apparatus for a non-thermal microwave polymerization effect induced by the electric fi eld, Polym. Chem. , 5 (2014) 5283-5288.
  • a specific example is a method in which an acid catalyst such as p-toluenesulfonic acid is added to 3-hydroxybutyric acid, and a dehydration esterification reaction is carried out in a solvent such as toluene at a temperature of 80 to 150°C. It will be done.
  • an acid catalyst such as p-toluenesulfonic acid
  • a dehydration esterification reaction is carried out in a solvent such as toluene at a temperature of 80 to 150°C. It will be done.
  • the lower limit of the number average molecular weight (Mn) of poly(3-hydroxybutyric acid) (PHB) may be 1,000 or more, 2,000 or more, 4,000 or more, 8,000 or more, and 10 ,000 or more, and the upper limit may be 1,000,000 or less, 500,000 or less, 100,000 or less, 50,000 or less, or 10,000 or less. Any combination of these upper and lower limits may be used.
  • the number average molecular weight (Mn) of poly(3-hydroxybutyric acid) (PHB) is 1,000,000 or more, the reaction with the polyester (PHA) of the hydroxyalkanoic acid (HA) or the former hydroxyalkanoic acid (HA) becomes extremely difficult.
  • the reaction may be carried out without a catalyst or in the presence of a catalyst.
  • the catalyst used in the reaction include metal catalysts, base catalysts, phosphine catalysts, and acid catalysts.
  • the metal catalyst include alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, titanium, etc.), Group 13 of the periodic table.
  • Examples include metal compounds containing metals (such as aluminum), metals from group 14 of the periodic table (germanium, tin, etc.), metals from group 15 of the periodic table (antimony, etc.), and the like.
  • the base catalyst examples include tertiary amines (trialkylamines such as trimethylamine and triethylamine), quaternary ammonium salts (tetraalkylammonium halides such as tetraethylammonium chloride and tetraethylammonium bromide, and benzyltrimethylammonium chloride). benzyltrialkylammonium halides, etc.).
  • phosphine catalyst examples include trialkylphosphines (trimethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, etc.), triarylphosphines (triphenylphosphine, tri(o- (tolyl) phosphine, etc.).
  • the acid catalyst examples include inorganic acids (for example, sulfuric acid, hydrogen chloride (or hydrochloric acid), nitric acid, phosphoric acid, etc.), organic acids (for example, sulfonic acids (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, etc.) alkanesulfonic acids, arenesulfonic acids such as p-toluenesulfonic acid), etc.).
  • the metal compounds include organic acid salts (acetate, propionate, etc.), inorganic acid salts (borate, carbonate, etc.), metal oxides (germanium oxide, etc.), metal chlorides (tin chloride, etc.).
  • metal alkoxides titanium tetraalkoxide, titanium tetra t-butoxide, aluminum isopropoxide, zinc t-butoxide, potassium t-butoxide, etc.
  • alkyl metals titanium alkyl aluminum, etc.
  • the amount of catalyst used is usually in the range of 0.001 to 5.0% by mass based on the mass of 3-hydroxybutyric acid (3HB).
  • the reaction may be carried out in the presence or absence of a solvent.
  • solvents include hydrocarbons (aliphatic hydrocarbons such as hexane, octane, and cyclohexane, and aromatic hydrocarbons such as toluene, xylene mesitylene, tetralin, chlorobenzene, o-dichlorobenzene, and 1,2,4-trichlorobenzene).
  • Hydrogens halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc.), ethers (dioxane, tetrahydrofuran, diphenyl ether, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters (methyl acetate, ethyl acetate, etc.) , butyl acetate, etc.), amides (dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (dimethylsulfoxide, etc.), cellosolve acetates (C 1-4 alkyl, such as ethyl cellosolve acetate) cellosolve acetate, etc.). These solvents can be used alone or in combination.
  • the reaction atmosphere may be air or an inert gas (nitrogen, helium, etc.) atmosphere, and the reaction pressure may be normal pressure or reduced pressure.
  • the reaction can proceed more easily by distilling water generated in the esterification reaction out of the reaction system.
  • the method for producing the polyester (PHA) of hydroxyalkanoic acid (HA) is not particularly limited, and includes a method similar to the method for producing polylactic acid described in Non-Patent Document A mentioned above.
  • a method may be mentioned in which a sulfonic acid such as p-toluenesulfonic acid is added to a hydroxyalkanoic acid and a dehydration esterification reaction is carried out in a solvent such as toluene at a temperature of 80 to 160°C.
  • the lower limit of the number average molecular weight (Mn) of the polyester (PHA) of hydroxyalkanoic acid (HA) may be 1,000 or more, 2,000 or more, 4,000 or more, 8,000 or more, It may be 10,000 or more, and the upper limit may be 1,000,000 or less, 500,000 or less, 100,000 or less, 50,000 or less, or 10,000 or less. Any combination of these upper and lower limits may be used.
  • the number average molecular weight (Mn) of polyester (PHA) is 1,000,000 or less, the reaction with poly(3-hydroxybutyric acid) (PHB) tends to proceed.
  • the number average molecular weight (Mn) of the polyester (PHA) is 1,000 or more
  • the molecular weight and chain length of the copolyester of this embodiment may be reduced in the reaction with the poly(3-hydroxybutyric acid) (PHB). Control becomes easier.
  • the method for producing a copolyester of this embodiment (sometimes simply referred to as the production method of this embodiment) is a method for producing the copolyester of this embodiment described above.
  • the manufacturing method of the present embodiment includes a step of reacting poly(3-hydroxybutyric acid) (PHB) with the hydroxyalkanoic acid (HA) or the polyester (PHA) of the hydroxyalkanoic acid (HA).
  • PHB poly(3-hydroxybutyric acid)
  • HA hydroxyalkanoic acid
  • PHA hydroxyalkanoic acid
  • PHA hydroxyalkanoic acid
  • the manufacturing method of this embodiment preferably includes the following first and second steps.
  • First step performing an esterification reaction between the 3-hydroxybutyric acids to obtain the poly(3-hydroxybutyric acid) (PHB);
  • Second step A step of reacting the poly(3-hydroxybutyric acid) (PHB) obtained in the step 1 with the hydroxyalkanoic acid (HA) or the polyester (PHA) of the hydroxyalkanoic acid (HA).
  • Step 1A A step in which the hydroxyalkanoic acids (HA) are subjected to an esterification reaction to obtain a polyester (PHA) of the hydroxyalkanoic acids (HA).
  • the manufacturing method of this embodiment includes, for example, a mixed solution containing poly(3-hydroxybutyric acid) (PHB) and the hydroxyalkanoic acid (HA) or the polyester (PHA) of the hydroxyalkanoic acid (HA).
  • a method for obtaining the copolyester of the present embodiment by carrying out a transesterification reaction can be mentioned. Examples of the transesterification reaction include the method described in Non-Patent Document 1.
  • the method for producing the copolyester of the present embodiment includes, for example, a mixed solution containing poly(3-hydroxybutyric acid) (PHB) and a polyester (PHA) of hydroxyalkanoic acid (HA) such as lactic acid or polylactic acid.
  • a method for obtaining the copolyester of the present embodiment by carrying out a transesterification reaction can be mentioned.
  • the temperature of the transesterification reaction is preferably, for example, 90 to 200°C.
  • the manufacturing method of this embodiment uses a transesterification reaction between poly(3-hydroxybutyric acid) (PHB) and the polyester (PHA) of the hydroxyalkanoic acid (HA), the polyester (PHB) and the polyester (PHA)
  • the charging molar ratio is the content of the constituent units (3HB-U) of 3-hydroxybutyric acid (3HB) in the produced copolyester of this embodiment, and the average chain length of the constituent units of 3-hydroxybutyric acid (3HB) is , is not particularly limited as long as it falls within the above range.
  • the charged molar ratio of the structural unit (3HB-U) derived from polyester (PHB) and the structural unit (HA-U) derived from polyester (PHA) is 1 to 40 mol%, and 2 to 30 mol%. The amount is preferably from 3 to 25 mol%, and even more preferably from 4 to 20 mol%.
  • the charged molar ratio of the structural unit (3HB-U) derived from poly(3-hydroxybutyric acid) (PHB) and the structural unit (HA-U) derived from polyester (PHA) exceeds 40 mol%, 3-hydroxybutyric acid Acidic decomposition products of butyric acid are likely to be generated, causing problems such as unpleasant odors and easy hydrolysis.
  • the charged molar ratio of the structural unit (3HB-U) derived from polyester (PHB) to the structural unit (HA-U) derived from polyester (PHA) is less than 1, the biodegradability of the copolyester decreases.
  • titanium-based catalysts include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra n-propoxide, titanium tetra n-butoxide, tetrakis(2-ethylhexyloxy)titanium, tetrastearyloxytitanium, etc.
  • titanium tetraisopropoxide is preferred from the viewpoint of stability in handling and activity as a catalyst.
  • the amount of the catalyst used is usually 0.001 to 100% based on the total mass of poly(3-hydroxybutyric acid) (PHB) and the hydroxyalkanoic acid (HA) or the polyester of the hydroxyalkanoic acid (HA) (PHA).
  • the range is 5.0% by mass.
  • the reaction atmosphere may be air or an inert gas (nitrogen, helium, etc.) atmosphere, and the reaction pressure may be normal pressure or reduced pressure.
  • the reaction is carried out until the average chain length of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) is 2 to 20.
  • the reaction temperature is usually 80 to 250°C, preferably 100 to 200°C, more preferably 110 to 160°C, even more preferably 125 to 150°C.
  • the reaction time is usually 1 minute to 200 hours, preferably 5 minutes to 100 hours, more preferably 10 minutes to 80 hours, even more preferably 15 minutes to 60 hours.
  • transesterification and esterification can be performed simultaneously.
  • the chain length can be controlled by the transesterification reaction and polymerization growth can be performed simultaneously by the esterification reaction.
  • polyurethane As an application example of the copolyester of this embodiment, for example, a polyurethane derived from the copolyester of this embodiment (sometimes referred to as "polyurethane according to this embodiment") obtained using the copolyester of this embodiment is Can be mentioned.
  • the polyurethane according to this embodiment is obtained, for example, by reacting the copolyester of this embodiment with a polyisocyanate.
  • a polyol other than the copolyester of this embodiment, a chain extender, a chain terminator, and a crosslinking agent may be used in combination.
  • the copolyester of this embodiment for obtaining the polyurethane is preferably a polyester polyol.
  • the polyurethane according to this embodiment is obtained by reacting a polyol and a polyisocyanate, and at least the copolyester of this embodiment is used as the polyol. Therefore, polyurethane is a reaction product obtained by the reaction of polyol and polyisocyanate, and polyurethane has a structural unit derived from a polyol and a structural unit derived from a polyisocyanate, and at least a structural unit derived from the copolyester of this embodiment. has.
  • chain extenders include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, Aliphatic polyol compounds such as glycerin, sorbitol, and neopentyl glycol; Aromatic polyol compounds such as bisphenol A, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone; Water; ethylene diamine , 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4 , 4'-dicyclohexylmethan
  • the content of the copolyester of this embodiment in 100% by mass of the total polyol used in the polyurethane synthesis is preferably 10 to 100% by mass, more preferably 50 to 100% by mass.
  • polyisocyanate examples include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene Diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3- Dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5- Diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,
  • 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and toluene diisocyanate are more preferred.
  • chain terminator having one active hydrogen group may be used if necessary.
  • chain terminators include aliphatic monohydroxy compounds having a hydroxyl group such as methanol, ethanol, propanol, butanol and hexanol, and aliphatic monoamines having an amino group such as morpholine, diethylamine, dibutylamine, monoethanolamine and diethanolamine. is exemplified. These may be used alone or in combination of two or more.
  • a crosslinking agent having three or more active hydrogen groups or isocyanate groups can be used as necessary.
  • the polyurethane according to this embodiment can be obtained by a known polyurethane manufacturing method. Specifically, for example, a method of manufacturing by preparing a polyol, a polyisocyanate, and the chain extender and reacting them can be mentioned. These reactions are preferably carried out, for example, at a temperature of 50 to 100°C for 3 to 10 hours. Moreover, the reaction may be carried out in an organic solvent.
  • organic solvents examples include ketone solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and methyl isobutyl ketone; methyl formate; , ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate, sec-butyl acetate, and other ester solvents; and the like can be used. These organic solvents may be used alone or in combination of two or more.
  • ketone solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and
  • the content of the structural unit derived from the copolyester of this embodiment in 100% by mass of the polyurethane of this embodiment is preferably 10 to 98% by mass, more preferably 20 to 98% by mass. Thereby, there is a tendency for more favorable effects to be obtained.
  • the content of each structural unit in polyurethane is measured by NMR.
  • the lower limit of the number average molecular weight (Mn) of the polyurethane according to this embodiment may be 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, or 10,000 or more.
  • the upper limit may be 1,000,000 or less, 500,000 or less, 100,000 or less, 500,000 or less, or 15,000 or less. Any combination of these upper and lower limits may be used.
  • the number average molecular weight (Mn) of the polyurethane may be 5,000 to 1,000,000, 6,000 to 500,000, 7,000 to 100,000, or 8,000 to 500,000. It may be between 10,000 and 15,000. Within the above range, there is a tendency for more favorable effects to be obtained.
  • the number average molecular weight (Mn) of polyurethane is a value measured by GPC.
  • resin composition examples include the copolyester of this embodiment described above, a thermoplastic resin composition containing polyurethane, or a thermosetting resin composition.
  • thermoplastic resin composition When the resin composition of this embodiment is a thermoplastic resin composition, for example, other resins, crystallization nucleating agents, heat stabilizers, hydrolysis inhibitors, other additives, etc. may be added as necessary. may also be included.
  • the crystallization nucleating agent used in the thermoplastic resin composition according to the present embodiment may be any crystallization nucleating agent used for thermoplastic resins derived from biomass resources such as polylactic acid and polybutylene succinate. But that's fine.
  • a talc-based nucleating agent, a nucleating agent made of a metal salt-based material having a phenyl group, a nucleating agent made of a benzoyl compound, etc. are preferably used.
  • Other known crystallization nucleating agents such as lactate, benzoate, silica, and phosphate ester salts may also be used.
  • the thermoplastic resin composition of the present embodiment contains a phenolic antioxidant and a phosphite antioxidant as a heat stabilizer of the resin composition, and a carbodiimide compound-based hydrolysis inhibitor as a hydrolysis inhibitor, for example, It is preferable that the resin contains polycarbodiimide resin (trade name: Carbodilite, manufactured by Nisshinbo Chemical Co., Ltd.).
  • the heat stabilizer and hydrolysis inhibitor to be added may be one selected from the above three types of additives, but the above two types of heat stabilizer and hydrolysis inhibitor have different functions. , and those in which each additive is added together are preferred.
  • the amounts of the heat stabilizer and hydrolysis inhibitor to be added vary depending on the type, but are generally preferably about 0.1 parts by mass to 5 parts by mass, respectively, per 100 parts by mass of the thermoplastic resin composition.
  • thermoplastic resin composition of this embodiment may further contain a silicone flame retardant, an organic metal salt flame retardant, an organic phosphorus flame retardant, a metal oxide flame retardant, a metal hydroxide flame retardant, etc. is preferred. This improves flame retardancy and suppresses the spread of fire, and also improves the fluidity of the biodegradable resin composition, making it possible to ensure better moldability.
  • a filler can be added to the thermoplastic resin composition of this embodiment.
  • fillers include talc, mica, montmorillonite, kaolin, and the like. When these fillers serve as crystal nuclei, crystallization of the copolyester is promoted, and the impact strength and heat resistance of the molded article are improved. Moreover, the rigidity of the molded body can also be increased.
  • thermoplastic resin composition of this embodiment includes an antioxidant, an anti-blocking agent, a coloring agent, a flame retardant, a mold release agent, an antifogging agent, a surface wetting improver, an incineration aid, a lubricant, a dispersion aid, and various other additives.
  • Various additives such as surfactants, plasticizers, compatibilizers, weatherability improvers, ultraviolet absorbers, processing aids, antistatic agents, colorants, lubricants, and mold release agents can also be blended as appropriate.
  • any known plasticizer that is generally used as a polymer plasticizer can be used without particular limitation, such as polyester plasticizers, glycerin plasticizers, polyhydric carboxylic acid ester plasticizers, and polyalkylene glycol plasticizers. and epoxy plasticizers.
  • the compatibilizer is not particularly limited as long as it functions as a compatibilizer for copolymer A and copolymer B.
  • the compatibilizing agent include inorganic fillers, glycidyl compounds, polymer compounds grafted or copolymerized with acid anhydrides, and organometallic compounds, and one or more of these may be used. By kneading these materials, heat resistance, bending strength, impact strength, flame retardance, etc. are also improved, which further promotes their application to molded products such as casings for electronic devices such as notebook computers and mobile phones. Ru.
  • fillers can also be blended as fillers.
  • functional additives chemical fertilizers, soil conditioners, plant activators, etc. can also be added.
  • the fillers are broadly classified into inorganic fillers and organic fillers. These can also be used singly or as a mixture of two or more.
  • Inorganic fillers include anhydrous silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, and wollastenite.
  • silicates such as calcined perlite, calcium silicate, and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate, and calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, and barium sulfate, etc. can be mentioned.
  • the content of the inorganic filler is generally 1 to 80% by weight, preferably 3 to 70% by weight, and more preferably 5 to 60% by weight in the entire composition.
  • organic fillers include raw starch, processed starch, pulp, chitin/chitosan, coconut shell powder, wood powder, bamboo powder, bark powder, and powders such as kenaf and straw. These can also be used singly or as a mixture of two or more.
  • the amount of organic filler added is usually 0.01 to 70% by weight based on the total composition.
  • a horizontal cylindrical mixer a horizontal cylindrical mixer, a V-shaped mixer, a double cone mixer, a ribbon blender, a blender such as a super mixer, and various continuous mixers can be used.
  • a batch kneading machine such as a roll or internal mixer, a one-stage or two-stage continuous kneading machine, a twin-screw extruder, a single-screw extruder, or the like can be used.
  • the kneading method include a method in which various additives, fillers, and thermoplastic resins are added and blended after heating and melting the mixture. Further, blending oil or the like can also be used for the purpose of uniformly dispersing the various additives mentioned above.
  • thermosetting resin composition When the resin composition of this embodiment is a thermosetting resin composition, it may contain, for example, another resin, a copolyester of this embodiment having a reactive group such as a hydroxyl group or a carboxyl group, as a thermosetting resin main ingredient. , further includes a curing agent such as an isocyanate curing agent or a polyamine curing agent that can thermally react with the reactive group.
  • a curing agent such as an isocyanate curing agent or a polyamine curing agent that can thermally react with the reactive group.
  • Examples of the curing agent according to this embodiment include tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, etc., which have an aromatic structure in their molecular structure.
  • Polyisocyanates compounds in which some of the isocyanate groups of these polyisocyanates are modified with carbodiimide; allophanate compounds derived from these polyisocyanates; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanate)
  • Polyfunctional isocyanates such as polyisocyanates, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, piperazine, or Examples include polyethylene polyamines such as N-aminoalkylpiperazine having an alkyl chain having 2 to 6 carbon atoms, and amine compounds such as 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine or IPDA). It will be done.
  • IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine
  • the cured product of the resin composition of the present embodiment is a cured product of the resin composition as the thermoplastic resin composition described above or the resin composition as the thermosetting resin composition described above.
  • the copolyester herein can be used for various purposes. Specifically, it can be used in a wide range of applications, including artificial leather, synthetic leather, shoes, thermoplastic resins, foamed resins, thermosetting resins, paints, laminating adhesives, elastic fibers, urethane raw materials, automobile parts, and sporting goods. . Since the copolyester of this embodiment, which has excellent biodegradability, is used, the product for the above application has excellent biodegradability.
  • the polyurethane herein can be used for various purposes. Specifically, artificial leather, synthetic leather, shoes, thermoplastic resin, foamed resin, thermosetting resin, paint, laminating adhesive, vibration isolating material, damping material, automobile parts, sporting goods, fiber treatment agent, binder. It can be used for a wide range of purposes. Since the copolyester of this embodiment, which has excellent biodegradability, is used, the product for the above application has excellent biodegradability.
  • the resin composition herein can be used for various purposes. Specifically, artificial leather, synthetic leather, shoes, thermoplastic resin, foamed resin, thermosetting resin, paint, laminating adhesive, vibration isolating material, damping material, automobile parts, sporting goods, fiber treatment agent, binder. It can be used for a wide range of purposes. Since the copolyester of this embodiment, which has excellent biodegradability, is used, the product for the above application has excellent biodegradability.
  • the coating agent contains the copolyester of this embodiment, and further contains other components such as other resins, water, and organic solvents, if necessary.
  • Coatings can be applied onto a variety of substrates.
  • the coating agent is used, for example, to coat the surface of a base material of a food packaging container.
  • the base material include plastic films such as styrene resin films, polyolefin resin films, polyester resin films, and nylon resin films, or laminates thereof.
  • the base material include paper, metallized film, aluminum foil, and the like.
  • the coating agent is preferably used for biodegradable substrates. Examples of biodegradable substrates include paper, polyester films, polyolefin films, starch films, and the like.
  • the coating agent can be used as an ink, an adhesive, or the like.
  • the ink contains the copolyester of this embodiment and a colorant, and further contains other components such as a pigment dispersant, water, and an organic solvent, if necessary.
  • the ink is, for example, a printing ink.
  • the ink may be, for example, a water-based ink or an ink that does not contain water (solvent-based ink).
  • the adhesive contains the copolyester of this embodiment, and further contains other components such as other resins, curing agents, and organic solvents, if necessary.
  • the adhesive can also be used as a laminating adhesive composition used when laminating onto the various base materials mentioned above to produce composite films used primarily as packaging materials for foods, medicines, detergents, and the like.
  • Such adhesives include, for example, a two-component curing adhesive containing the copolyester of the present embodiment, a polyester polyol, and a polyisocyanate, or an acrylic resin, a urethane resin, or an ethylene-vinyl acetate copolymer.
  • One-component adhesive can be used. These adhesives may be solvent-based, non-solvent-based, water-based, or alcohol-based adhesives, as required.
  • the sheet is made using a resin composition containing the copolyester of this embodiment.
  • the resin composition may contain other resins and various additives in addition to the copolyester of this embodiment.
  • various additives include plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants, antiblocking agents, heat stabilizers, and the like.
  • the sheet include a non-stretched sheet, a biaxially stretched sheet, and a foamed sheet.
  • the sheet can be used in a wide variety of applications, including, but not limited to, food packaging containers, construction materials, home appliances, and miscellaneous goods.
  • the film is made using a resin composition containing the copolyester of this embodiment.
  • the resin composition may contain other resins and various additives in addition to the copolyester of this embodiment.
  • various additives include plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants, antiblocking agents, heat stabilizers, and the like.
  • the film include unstretched film, biaxially stretched film, uniaxially stretched film, etc., and can be produced by, for example, melting pellets of film raw material in an extruder and then forming into a film using a T-die or inflation method. .
  • T-die method a biaxially stretched film is obtained by performing longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter.
  • the laminate includes at least one member selected from the sheets and films of this embodiment, and further includes other components such as a printed layer and a resin film as necessary.
  • the laminate is obtained, for example, by laminating a film or sheet on one or both sides of at least one selected from the sheets and films of the present embodiment in order to improve mechanical strength and chemical resistance. Specifically, it can be obtained by thermally laminating a polystyrene-based blown film on at least one of the front side and back side of a sheet or film, or by bonding an olefin-based film (CPP) using an adhesive.
  • the adhesive used is not particularly limited, and may be, for example, the adhesive of this embodiment or a known adhesive.
  • the molded product is obtained by molding at least one member selected from the sheet, film, and laminate of this embodiment.
  • the molded body is obtained, for example, by thermoforming the sheet, film, and laminate of this embodiment.
  • the thermoforming method include a hot plate contact thermoforming method, a vacuum forming method, a vacuum pressure forming method, a plug assist molding method, etc.
  • indirect heat forming using an infrared heater as a heat source can be preferably used. .
  • the molecular weight of the resin is a value measured using gel permeation chromatography (GPC) under the following conditions.
  • measuring device System Controller Waters 600 Controller Liquid pump Waters Model Code 60F RI (differential refractometer) detector Waters 2414 Autosampler Waters 717plus Autosampler
  • FIG. 2 is a 13 C-NMR spectrum of the copolyester of Example 1.
  • Non-patent Document B Hideki Abe, Yoshiharu Doi, Yoji Hori, Toshimitsu Hagiwara, Physical properties and enzymati c degradability of copolymers of (R)-3-hydroxybutyric acid and (S,S)-lactide, Polymer 1998, 39 (1) , 59-67.
  • Average chain length of 3HB 1 + 2 ⁇ (integral value of 3HB dyad of 19.8 ppm) / (integral value of 3HB-lactic acid dyad of 19.6 ppm + integral value of lactic acid-3HB dyad of 40.5 ppm)
  • Biodegradability evaluation method was evaluated with reference to the method described in "2.3. Biodegradation with seawater by BOD method" of Non-Patent Document C below. In addition, the evaluation method of Non-Patent Document C was tested by replacing activated sludge with seawater as the inoculum source according to JIS K6950.
  • Non-patent Document C Atsuyoshi Nakayama*, Naoko Yamano, Norioki Kawasaki, Biodegradation in seawater of aliphatic Polyesters, Polymer Degradation and Stability 166 (2019) 290-299.
  • Biodegradability (%) (BOD 0 - BOD B )/ThOD ⁇ 100
  • BOD 0 Biochemical oxygen demand of test material (measured value: mg)
  • BOD B Average biochemical oxygen demand of blank test (measured value: mg)
  • ThOD Theoretical oxygen demand required if the test material is completely oxidized (calculated value: mg)
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 5,800, and the weight average molecular weight Mw was 11,500.
  • Example 1 In a test tube equipped with a stirrer and a nitrogen gas inlet tube, 5.20 g (0.0500 mol) of 3-hydroxybutyric acid, 52 mL of toluene, and 0.475 g (0.00250 mol) of p-toluenesulfonic acid were added, and while removing water, Polymerization was carried out at °C for 4 hours. 21.1 g (0.199 mol) of an 85% aqueous lactic acid solution was added to a test tube containing poly(3-hydroxybutyric acid), and the mixture was reacted at 115° C. for 52 hours while removing water.
  • the reaction solution was cooled to room temperature, 100 mL of methanol was added to precipitate a solid, and the mixture was filtered to obtain a 3-hydroxybutyric acid-lactic acid copolyester as the copolyester of this embodiment.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 7,100, and the weight average molecular weight Mw was 10,100.
  • the content of the structure derived from 3-hydroxybutyric acid was measured by the method described in ⁇ Calculation of 3-hydroxybutyric acid content> above. The results are shown in Table 1.
  • the average chain length of the structure derived from 3-hydroxybutyric acid was measured by the method described in ⁇ Evaluation of Average Chain Length> above. The results are shown in Table 1.
  • Biodegradability was evaluated by the method described in ⁇ Biodegradability Evaluation> above. The results are shown in Table 1.
  • Example 2 In a test tube equipped with a stirrer and a nitrogen gas inlet tube, 5.20 g (0.0500 mol) of 3-hydroxybutyric acid, 52 mL of toluene, and 0.475 g (0.00250 mol) of p-toluenesulfonic acid were added, and while removing water, Polymerization was carried out at °C for 22 hours. 21.1 g (0.199 mol) of an 85% aqueous lactic acid solution was added to a test tube containing poly(3-hydroxybutyric acid), and the mixture was reacted at 115° C. for 33 hours while removing water.
  • the reaction solution was cooled to room temperature, 100 mL of methanol was added to precipitate a solid, and the mixture was filtered to obtain a 3-hydroxybutyric acid-lactic acid copolyester as the copolyester of this embodiment.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 6,900, and the weight average molecular weight Mw was 9,000.
  • the content of 3-hydroxybutyric acid, average chain length, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 In a test tube equipped with a stirrer and a nitrogen gas inlet tube, 2.08 g (0.0200 mol) of 3-hydroxybutyric acid, 46 mL of toluene, and 0.380 g (0.00200 mol) of p-toluenesulfonic acid were added, and while removing water, Polymerization was carried out at °C for 5 hours. 19.1 g (0.180 mol) of an 85% aqueous lactic acid solution was added to a test tube containing poly(3-hydroxybutyric acid), and the mixture was reacted at 115° C. for 33 hours while removing water.
  • the reaction solution was cooled to room temperature, 100 mL of methanol was added to precipitate a solid, and the mixture was filtered to obtain a 3-hydroxybutyric acid-lactic acid copolyester as the copolyester of this embodiment.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 6,900, and the weight average molecular weight Mw was 12,000.
  • the content of 3-hydroxybutyric acid, average chain length, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 In a test tube equipped with a stirrer and a nitrogen gas introduction tube, 2.08 g (0.0200 mol) of 3-hydroxybutyric acid, 43 mL of toluene, and 0.380 g (0.00200 mol) of p-toluenesulfonic acid were added, and while removing water, Polymerization was carried out at °C for 10 hours. 19.1 g (0.180 mol) of an 85% aqueous lactic acid solution was added to a test tube containing poly(3-hydroxybutyric acid), and the mixture was reacted at 115° C. for 33 hours while removing water.
  • the reaction solution was cooled to room temperature, 100 mL of methanol was added to precipitate a solid, and the mixture was filtered to obtain a 3-hydroxybutyric acid-lactic acid copolyester as the copolyester of this embodiment.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 7,000, and the weight average molecular weight Mw was 11,000.
  • the content of 3-hydroxybutyric acid, average chain length, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the reaction solution was cooled to room temperature, 100 mL of methanol was added, and filtration was performed to obtain a 3-hydroxybutyric acid-lactic acid copolyester.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 9,800, and the weight average molecular weight Mw was 19,500.
  • the content of 3-hydroxybutyric acid, average chain length, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 6,100, and the weight average molecular weight Mw was 11,500.
  • the content of 3-hydroxybutyric acid, average chain length, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the copolyester of this embodiment has a structure derived from 3-hydroxybutyric acid and exhibits biodegradability, so the resin composition containing the copolyester of this embodiment can be used as a sustainable product group (packaging materials, films). It is expected that it will be used for various purposes such as

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001002763A (ja) * 1999-06-18 2001-01-09 Daicel Chem Ind Ltd ラクチド／ラクトン共重合体及びその製造方法
JP2004137490A (ja) * 2002-09-24 2004-05-13 Asahi Kasei Chemicals Corp グリコール酸共重合体及びその製造方法
JP2005501927A (ja) * 2001-04-20 2005-01-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 核剤および可塑剤を用いたポリヒドロキシアルカノエートの加工
JP2005533148A (ja) * 2002-07-16 2005-11-04 インノコア テクノロジーズ ビー．ブイ． 生分解性の相分離したセグメント化多ブロック共重合体
JP2009500468A (ja) * 2005-07-04 2009-01-08 エルジー・ケム・リミテッド 形状記憶効果を有するポリ（３−ヒドロキシアルカノエート）ブロックコポリマー
CN104448258A (zh) * 2014-11-18 2015-03-25 中国科学院微生物研究所 一种phbv聚合物、制备方法及利用phbv聚合物制作的止血材料
US20170044326A1 (en) * 2014-04-17 2017-02-16 Regents Of The University Of Minnesota Poly(beta-methyl-delta-valerolactone) block polymers
JP2018109103A (ja) * 2016-12-28 2018-07-12 国立大学法人北海道大学 ブロック共重合体及びこれを含む樹脂組成物、並びにブロック共重合体の製造方法
US20210077667A1 (en) * 2017-08-31 2021-03-18 University Of Westminster Stents

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001002763A (ja) * 1999-06-18 2001-01-09 Daicel Chem Ind Ltd ラクチド／ラクトン共重合体及びその製造方法
JP2005501927A (ja) * 2001-04-20 2005-01-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 核剤および可塑剤を用いたポリヒドロキシアルカノエートの加工
JP2005533148A (ja) * 2002-07-16 2005-11-04 インノコア テクノロジーズ ビー．ブイ． 生分解性の相分離したセグメント化多ブロック共重合体
JP2004137490A (ja) * 2002-09-24 2004-05-13 Asahi Kasei Chemicals Corp グリコール酸共重合体及びその製造方法
JP2009500468A (ja) * 2005-07-04 2009-01-08 エルジー・ケム・リミテッド 形状記憶効果を有するポリ（３−ヒドロキシアルカノエート）ブロックコポリマー
US20170044326A1 (en) * 2014-04-17 2017-02-16 Regents Of The University Of Minnesota Poly(beta-methyl-delta-valerolactone) block polymers
CN104448258A (zh) * 2014-11-18 2015-03-25 中国科学院微生物研究所 一种phbv聚合物、制备方法及利用phbv聚合物制作的止血材料
JP2018109103A (ja) * 2016-12-28 2018-07-12 国立大学法人北海道大学 ブロック共重合体及びこれを含む樹脂組成物、並びにブロック共重合体の製造方法
US20210077667A1 (en) * 2017-08-31 2021-03-18 University Of Westminster Stents

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