WO2024225442A1 - （メタ）アクリル酸化合物の製造方法 - Google Patents

（メタ）アクリル酸化合物の製造方法 Download PDF

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WO2024225442A1
WO2024225442A1 PCT/JP2024/016469 JP2024016469W WO2024225442A1 WO 2024225442 A1 WO2024225442 A1 WO 2024225442A1 JP 2024016469 W JP2024016469 W JP 2024016469W WO 2024225442 A1 WO2024225442 A1 WO 2024225442A1
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polymer
meth
acid
hydroxycarboxylic acid
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良一 赤石
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Osaka Organic Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid

Definitions

  • the present invention relates to a method for producing a (meth)acrylic acid compound.
  • (Meth)acrylic acid compounds are compounds that are widely used as raw materials for synthesizing poly(meth)acrylic acid resins.
  • As a method for producing (meth)acrylic acid compounds methods using a polymer of 3-hydroxycarboxylic acid as a raw material have been investigated.
  • a method for producing (meth)acrylic acid by heating and/or contacting with a catalyst a composition containing a specific polymer of 3-hydroxycarboxylic acid Patent Document 1
  • a method for producing (meth)acrylic acid by heating a raw material composition containing a predetermined amount of polymer of 3-hydroxycarboxylic acid to produce a gaseous decomposition product of the polymer of 3-hydroxycarboxylic acid and contacting the decomposition product with a dehydration catalyst Patent Document 2
  • a method for producing (meth)acrylic acid by heating a raw material composition containing a predetermined amount of polymer of 3-hydroxycarboxylic acid having a degree of 3 to 20 Patent Document 3
  • the objective of the present invention is to provide a novel method for producing (meth)acrylic acid compounds from hydroxycarboxylic acids and/or their polymers.
  • the inventors conducted extensive research into a method for producing (meth)acrylic acid from a composition containing a hydroxycarboxylic acid and/or a polymer thereof, and as a result discovered that a (meth)acrylic acid compound can be produced by heating and reacting a mixture containing a hydroxycarboxylic acid and/or a polymer thereof, a basic catalyst, and a carboxylic acid anhydride, thus completing the present invention.
  • a method for producing a (meth)acrylic acid compound using a hydroxycarboxylic acid and/or a polymer thereof as a raw material comprising the steps of: a hydroxycarboxylic acid and/or a polymer thereof; A basic catalyst; The method includes at least a reaction step of heating a mixture containing the above to react and generate a (meth)acrylic acid compound, (1) the mixture further comprises a carboxylic acid anhydride; and/or (2) A production method in which the weight-average molecular weight of the polymer of hydroxycarboxylic acid contained in the raw material is 10,000 or more.
  • a method for producing a (meth)acrylic acid compound using a 3-hydroxycarboxylic acid and/or a polymer thereof as a raw material comprising the steps of: 3-hydroxycarboxylic acid and/or polymer thereof, A basic catalyst; A carboxylic acid anhydride, The method for producing a (meth)acrylic acid compound according to [1], further comprising at least a reaction step of heating a mixture containing the above.
  • the hydroxycarboxylic acid is at least one selected from the group consisting of 2-hydroxycarboxylic acids and 3-hydroxycarboxylic acids.
  • the present invention provides a novel production method that makes it possible to produce (meth)acrylic acid compounds from hydroxycarboxylic acids and/or their polymers.
  • FIG. 1 is a HPLC chart of the raw material (A) containing 3-hydroxypropionic acid and its polymer obtained in Production Example 1.
  • FIG. 1 shows an HPLC chart of the reaction product (1) obtained in Example 1.
  • FIG. 2 is a HPLC chart of the distillate obtained in Example 3.
  • FIG. 1 is a diagram showing the 1 H-NMR chart of the distillate obtained in Example 3.
  • FIG. 2 shows an HPLC chart of the reaction product (3) obtained in Example 3.
  • FIG. 1 is a 1 H-NMR chart of the reaction product (3) obtained in Example 3.
  • the production method of the present invention is a method for producing a (meth)acrylic acid compound using a hydroxycarboxylic acid and/or a polymer thereof as a raw material, comprising the steps of: a hydroxycarboxylic acid and/or a polymer thereof; A basic catalyst;
  • the method includes at least a reaction step of heating a mixture containing the above to react and generate a (meth)acrylic acid compound, (1) the mixture further comprises a carboxylic acid anhydride; and/or (2)
  • a production method in which the weight-average molecular weight of the polymer of the hydroxycarboxylic acid contained in the raw material is 10,000 or more.
  • the raw material hydroxycarboxylic acid and/or its polymer and a basic catalyst react with a carboxylic anhydride, as the case may be, to produce a (meth)acrylic acid compound.
  • the production method of the present invention may satisfy the above (1), may satisfy (2), or may satisfy both (1) and (2).
  • the hydroxycarboxylic acid include 2-hydroxycarboxylic acid and 3-hydroxycarboxylic acid.
  • 2-hydroxycarboxylic acid and its polymer, 3-hydroxycarboxylic acid and its polymer, polymer of 2-hydroxycarboxylic acid and 3-hydroxycarboxylic acid, and mixtures thereof can be suitably used.
  • a polymer of a 2-hydroxycarboxylic acid having a weight-average molecular weight of 10,000 or more, a polymer of a 3-hydroxycarboxylic acid having a weight-average molecular weight of 10,000 or more, a polymer of a 2-hydroxycarboxylic acid and a 3-hydroxycarboxylic acid having a weight-average molecular weight of 10,000 or more, and a mixture of these can be preferably used.
  • the present inventors have found that in a method for producing a (meth)acrylic acid compound using a hydroxycarboxylic acid and/or a polymer thereof as a raw material, the reaction for giving a (meth)acrylic acid compound from the hydroxycarboxylic acid and/or a polymer thereof used as the raw material proceeds efficiently when (1) a carboxylic acid anhydride is further contained, and/or (2) the weight-average molecular weight of the polymer of the hydroxycarboxylic acid contained in the raw material is 10,000 or more.
  • the production method of the present invention is a production method for a (meth)acrylic acid compound using a 3-hydroxycarboxylic acid and/or a polymer thereof as a raw material, comprising the steps of: 3-hydroxycarboxylic acid and/or polymer thereof, A basic catalyst; A carboxylic acid anhydride,
  • the production method includes at least a reaction step of heating a mixture containing the above to react and produce a (meth)acrylic acid compound.
  • the hydroxycarboxylic acid and/or its polymer is a component that serves as a raw material for providing a (meth)acrylic acid compound.
  • at least one of the hydroxycarboxylic acid and/or its polymer may be used, and only the hydroxycarboxylic acid may be used, only the polymer of the hydroxycarboxylic acid may be used, or a mixture of the hydroxycarboxylic acid and the polymer of the hydroxycarboxylic acid may be used.
  • the hydroxycarboxylic acid may be one kind of hydroxycarboxylic acid or a mixture of two or more kinds of hydroxycarboxylic acids.
  • the polymer of the hydroxycarboxylic acid may also be one kind or two or more kinds of hydroxycarboxylic acid polymers, and the degree of polymerization may be one kind or two or more kinds.
  • 3-Hydroxycarboxylic acids are compounds that have a carboxylic acid group and at least a hydroxyl group at the ⁇ -position of the carbonyl carbon of the carboxylic acid group.
  • Examples of 3-hydroxycarboxylic acids include 3-hydroxypropionic acid, 3-hydroxybutanoic acid, 3-hydroxypentanoic acid, 3-hydroxyhexanoic acid, and compounds in which the hydrogen atom bonded to the carbon atom of the above 3-hydroxycarboxylic acids has been replaced with a substituent such as an alkyl group.
  • Polymers of 3-hydroxycarboxylic acids are, for example, polymers in which two or more 3-hydroxycarboxylic acids are bonded to each other via intermolecular ester bonds.
  • a 2-hydroxycarboxylic acid is a compound that has a carboxylic acid group and at least a hydroxyl group at the alpha position of the carbonyl carbon of the carboxylic acid group.
  • Examples of 2-hydroxycarboxylic acids include 2-hydroxypropionic acid, 2-hydroxybutanoic acid, 2-hydroxyisobutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, and compounds in which the hydrogen atom bonded to the carbon atom of the above 2-hydroxycarboxylic acid is replaced with a substituent such as an alkyl group.
  • a polymer of 2-hydroxycarboxylic acid is, for example, a polymer in which two or more 2-hydroxycarboxylic acids are bonded to each other via intermolecular ester bonds.
  • the hydroxycarboxylic acid polymer may be any polymer in which two or more hydroxycarboxylic acids are polymerized, for example, a multimer in which two or more hydroxycarboxylic acids are ester-linked.
  • the degree of polymerization and distribution of the multimer are not particularly limited.
  • the hydroxycarboxylic acid polymer may be composed of one type of hydroxycarboxylic acid, or may be composed of two or more types of hydroxycarboxylic acids, or may contain structural units other than hydroxycarboxylic acids. From the viewpoint of efficiently producing (meth)acrylic acid compounds, it is preferable that the hydroxycarboxylic acid polymer contains only hydroxycarboxylic acids as structural units.
  • the degree of polymerization of the hydroxycarboxylic acid polymer that can be contained in the mixture is not particularly limited, and polymers having various degrees of polymerization may be used as a raw material.
  • the degree of polymerization of the hydroxycarboxylic acid may be, for example, 2-30,000-mer, etc., from the viewpoint of availability and manufacturability.
  • the content of the 2-30,000-mer of the hydroxycarboxylic acid relative to a total of 100 parts by mass of the hydroxycarboxylic acid and/or a polymer thereof is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
  • the content of the 2-20,000-mer, more preferably 2-15,000-mer, and even more preferably 2-10,000-mer of the 3-hydroxycarboxylic acid is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, relative to a total of 100 parts by mass of the hydroxycarboxylic acid and a polymer thereof.
  • the content of each polymer relative to 100 parts by mass of the total of the hydroxycarboxylic acid and its polymer can be calculated, for example, by HPLC, 1 H-NMR, or the like.
  • the content of the dimer to 20mer of the hydroxycarboxylic acid relative to the total 100 parts by mass of the hydroxycarboxylic acid and its polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
  • the content of the dimer to 15mer, more preferably the dimer to 10mer of the hydroxycarboxylic acid is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, relative to the total 100 parts by mass of the hydroxycarboxylic acid and its polymer.
  • the content of each multimer relative to the total 100 parts by mass of the hydroxycarboxylic acid and its polymer can be calculated, for example, from HPLC, 1 H-NMR, or the like.
  • 3-hydroxycarboxylic acids and polymers thereof include Formula (III)-1: [In formula (III)-1, R 4 to R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 or more]
  • the compound may be represented by the formula:
  • the 3-hydroxycarboxylic acid has the formula (II)-1: [In formula (II)-1, R 4 to R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]
  • the compound in which n is 2 or more in the formula (III)-1 is a polymer of a 3-hydroxycarboxylic acid represented by the formula (II)-1.
  • R 4 to R 6 in formula (II)-1 and formula (III)-1 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • R 4 to R 6 each independently represent preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 4 represents a hydrogen atom.
  • R 5 and R 6 each independently represent preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • the 3-hydroxycarboxylic acid of formula (II)-1 in which R 4 to R 6 each represent a hydrogen atom is also called 3-hydroxypropionic acid.
  • n in formula (III)-1 is not particularly limited as long as it is 1 or more, and it is considered that 3-hydroxycarboxylic acid and its polymers usually contain multiple types of compounds or polymers with different n.
  • the upper limit of n is not particularly limited, and may be, for example, 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 5,000 or less, 3,000 or less, 1,000 or less, 500 or less, etc.
  • the upper limit of n is not particularly limited, but from the viewpoint of easily enhancing the effect of further including a carboxylic acid anhydride, it may be, for example, 100 or less, 80 or less, 60 or less, 50 or less, 40 or less, 30 or less, etc.
  • 2-hydroxycarboxylic acids and polymers thereof include Formula (III)-2: [In formula (III)-2, R 10 and R 11 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 or more]
  • the compound may be represented by the formula:
  • the 2-hydroxycarboxylic acid has the formula (II)-2: [In formula (II)-2, R 12 and R 13 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]
  • the compound in which n is 2 or more in formula (III)-2 is a polymer of a 2-hydroxycarboxylic acid represented by formula (II)-2.
  • R 10 to R 13 in formula (II)-2 and formula (III)-2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • R 10 to R 13 each independently preferably represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • R 10 and R 11 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 10 and R 11 each preferably represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.
  • the 2-hydroxycarboxylic acid of formula (II)-2 in which R 12 is CH 2 and R 13 is a methyl group is also called 2-hydroxyisobutanoic acid.
  • n is not particularly limited as long as it is 1 or more, and it is considered that 2-hydroxycarboxylic acid and its polymers usually contain multiple types of compounds or polymers with different n.
  • the upper limit of n is not particularly limited, and may be, for example, 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 5,000 or less, 3,000 or less, 1,000 or less, 500 or less, etc.
  • the upper limit of n is not particularly limited, but from the viewpoint of easily enhancing the effect of further including a carboxylic acid anhydride, it may be, for example, 100 or less, 80 or less, 60 or less, 50 or less, 40 or less, 30 or less, etc.
  • the production method of the present invention is a production method for a (meth)acrylic acid compound using a hydroxycarboxylic acid and/or a polymer thereof as a raw material, comprising the steps of: a hydroxycarboxylic acid and/or a polymer thereof; A basic catalyst;
  • the method includes at least a reaction step of heating a mixture containing the above-mentioned hydroxycarboxylic acid to react with the above-mentioned hydroxycarboxylic acid to produce a (meth)acrylic acid compound, and the weight-average molecular weight of the polymer of the hydroxycarboxylic acid contained in the raw material is 10,000 or more.
  • the embodiment (2) in which the weight-average molecular weight of the polymer of the hydroxycarboxylic acid contained in the raw material is 10,000 or more will be described below.
  • the weight-average molecular weight of a polymer of a hydroxycarboxylic acid contained in the raw material is 10,000 or more, it is possible to produce a (meth)acrylic acid compound from a hydroxycarboxylic acid and/or its polymer even when the mixture does not further contain a carboxylic acid anhydride.
  • the mixture further contains a carboxylic acid anhydride, it is possible to produce a (meth)acrylic acid compound more efficiently.
  • the weight-average molecular weight of the polymer of the hydroxycarboxylic acid contained in the raw material is 10,000 or more.
  • the characteristics of the hydroxycarboxylic acid and its polymer described in the embodiment (1) above also apply to the embodiment (2) as long as they are not inconsistent with this characteristic.
  • the weight-average molecular weight of the polymer of the hydroxycarboxylic acid contained in the raw material is preferably 20,000 or more, more preferably 60,000 or more, even more preferably 70,000 or more, particularly preferably 100,000 or more, and most preferably 130,000 or more.
  • the upper limit of the weight-average molecular weight of the polymer of the hydroxycarboxylic acid is not particularly limited, but may be, for example, 1,000,000 or less, more preferably 800,000 or less.
  • Whether the weight-average molecular weight of the polymer of hydroxycarboxylic acid contained in the raw material is 10,000 or more can be determined, for example, by using the 3-hydroxycarboxylic acid and/or its polymer used as the raw material as a measurement sample and measuring the weight-average molecular weight in terms of polystyrene by gel permeation chromatography (GPC).
  • the measurement conditions for the weight-average molecular weight include those described in the Examples.
  • the method for producing the hydroxycarboxylic acid is not particularly limited, and the hydroxycarboxylic acid can be produced by a known method.
  • the method for producing the polymer of 3-hydroxycarboxylic acid is not particularly limited.
  • the polymer may be chemically synthesized by intermolecular bonding of 3-hydroxycarboxylic acid, or a polymer of 3-hydroxycarboxylic acid produced through a fermentation process may be used.
  • a polymer of 3-hydroxycarboxylic acid produced by a method such as that described in WO 2011/100608 can be used.
  • the 3-hydroxycarboxylic acid polymer may be added to the mixture in the production method of the present invention, for example, in the form of a composition containing the 3-hydroxycarboxylic acid polymer and other by-products obtained during the production of the 3-hydroxycarboxylic acid polymer.
  • the polymer When a polymer of 3-hydroxycarboxylic acid is produced through a fermentation process, the polymer can be produced by producing 3-hydroxycarboxylic acid by a method described in WO 2011/100608, WO 2002/42418, or the like, and dehydrating and condensing the obtained 3-hydroxycarboxylic acid by the above-mentioned dehydration condensation method.
  • it can also be produced using glucose, glycerol, or the like as a raw material, as disclosed in Front. Bioeng. Biotechnol., 9:646995 (2021).
  • the method for producing the polymer of 2-hydroxycarboxylic acid is not particularly limited.
  • the polymer may be chemically synthesized by intermolecular bonding of 2-hydroxycarboxylic acid, or a polymer of 2-hydroxycarboxylic acid produced through a fermentation process may be used.
  • the 2-hydroxycarboxylic acid polymer may be added to the mixture in the production method of the present invention, for example, in the form of a composition containing the 2-hydroxycarboxylic acid polymer obtained during the production of the 2-hydroxycarboxylic acid polymer and other by-products.
  • the polymer can be produced by producing 2-hydroxycarboxylic acid by the method described in Applied and Environmental Microbiology, 2017, 83(3), e02622-16, etc., and polymerizing the obtained 2-hydroxycarboxylic acid via the lactide derivative described above.
  • the method for producing a polymer of hydroxycarboxylic acid having a weight-average molecular weight of 10,000 or more is not particularly limited, but may be the method described in the Examples.
  • the basic catalyst acts as a catalyst when a (meth)acrylic acid compound is produced using a hydroxycarboxylic acid and/or its polymer as a raw material.
  • the basic catalyst may be a basic substance that acts as a catalyst, and may be a compound that contains a basic site in its molecular structure.
  • the basic catalyst is not particularly limited, and may be either soluble or insoluble in the reaction mixture.
  • the acid dissociation constant pKa of the basic catalyst is preferably 0.5 to 40, more preferably 1 to 30, even more preferably 2 to 15, and particularly preferably 3 to 7.
  • the pKa of the basic catalyst in the present invention refers to the pKa of the conjugate acid, and may be determined by performing acid-base titration on the conjugate acid, but the pKa listed in Tables 10 and 19 listed on pages II-317 to II-321 of the Basic Handbook, Revised 4th Edition may also be used.
  • Specific examples of the basic catalyst include carboxylates, amines, inorganic hydroxides, ammonium hydroxides, metal amides, and metal alkoxides, and preferably carboxylates.
  • the basic catalyst include alkali metal carboxylates (alkali metal salts of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, alkali metal salts of aliphatic carboxylic acids, etc.), quaternary ammonium carboxylates (quaternary ammonium salts of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, quaternary ammonium salts of aliphatic carboxylic acids, etc.), ammonium betaine, alkali metal hydroxides (e.g., potassium hydroxide, sodium hydroxide, lithium hydroxide, etc.), alkaline earth metal hydroxides (magnesium hydroxide, calcium hydroxide, etc.), transition metal hydroxides (copper hydroxide, etc.), alkali metal carbonates (potassium carbonate, sodium carbonate, lithium carbonate, etc.), alkaline earth metal carbonates (magnesium carbonate, calcium carbonate, etc.), and the like.
  • alkali metal hydroxides
  • organic solvent examples include magnesium, calcium carbonate, barium carbonate, etc.), alkali metal hydrogen carbonates (potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, etc.), alkaline earth metal hydrogen carbonates (magnesium hydrogen carbonate, calcium hydrogen carbonate, barium hydrogen carbonate, etc.), alkoxides (for example, alkali metal alkoxides such as potassium methoxide and sodium methoxide), alkali metal amides (potassium amide, sodium amide, etc.), amines or ammoniums (alkylamines such as triethylamine; tertiary arylamines such as N,N-dimethylaniline), heterocyclic amines such as pyridine, and quaternary ammonium hydroxides.
  • alkali metal alkoxides such as potassium methoxide and sodium methoxide
  • alkali metal amides potential amide, sodium amide, etc.
  • amines or ammoniums alkyl
  • the basic catalyst may be preferably a carbonate or a hydrogen carbonate, and more preferably at least one selected from the group consisting of an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal hydrogen carbonate, and an alkaline earth metal carbonate. More specifically, the above-mentioned ones can be mentioned.
  • the carbonate ion or hydrogen carbonate ion disappears from the reaction system as carbon dioxide during the reaction, while the remaining alkali metal ion becomes the alkali metal salt of the desired ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and is thought to act as a catalyst.
  • the basic catalyst may be preferably an alkali metal salt of a carboxylate, more preferably at least one selected from the group consisting of an alkali metal salt of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and an alkali metal salt of an aliphatic carboxylic acid, and even more preferably at least one selected from the group consisting of an alkali metal salt of an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid and an alkali metal salt of an aliphatic monocarboxylic acid.
  • An example of the alkali metal salt of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is an alkali metal salt of (meth)acrylic acid.
  • alkali metal examples include lithium, sodium, potassium, etc., and are preferably sodium or potassium. More specifically, examples of the alkali metal salt of an aliphatic carboxylic acid include potassium (meth)acrylate and sodium (meth)acrylate. Examples of the alkali metal salt of an aliphatic carboxylic acid include potassium acetate and sodium acetate.
  • an alkali metal salt of an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid is used as the alkali metal salt of a carboxylate, an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid derived from the alkali metal salt of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid is produced.
  • the structure of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid in the alkali metal salt of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid is made the same as that of the (meth)acrylic acid compound obtained by the production method of the present invention, the amount of impurities that may be contained in the (meth)acrylic acid compound obtained by the production method of the present invention can be reduced.
  • an alkali metal salt of an aliphatic carboxylic acid preferably an alkali metal salt of an aliphatic monocarboxylic acid
  • an aliphatic (mono)carboxylic acid is generated as a by-product. Since an aliphatic (mono)carboxylic acid is easily removed by distillation or washing with water, the amount of impurities that may be contained in the (meth)acrylic acid compound obtained by the production method of the present invention can be greatly reduced.
  • At least one selected from the group consisting of alkali metal salts of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and alkali metal salts of aliphatic carboxylic acids as the basic catalyst, and more preferably to use at least one selected from the group consisting of alkali metal salts of (meth)acrylic acid and alkali metal salts of aliphatic carboxylic acids, since this makes it possible to greatly reduce the amount of impurities that may be contained in the (meth)acrylic acid compound obtained by the production method of the present invention.
  • the basic catalyst may be preferably a quaternary ammonium salt of a carboxylic acid, more preferably at least one selected from the group consisting of a quaternary ammonium salt of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and a quaternary ammonium salt of an aliphatic carboxylic acid, and even more preferably at least one selected from the group consisting of a quaternary ammonium salt of an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid and a quaternary ammonium salt of an aliphatic monocarboxylic acid.
  • Examples of the quaternary ammonium salt of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid include an alkali metal salt of (meth)acrylic acid.
  • Examples of the ammonium ion of such a quaternary ammonium salt include an ammonium ion represented by N + (-R a ) 4 [wherein R a each independently represents a hydrocarbon group which may have a substituent (e.g., an aromatic substituent such as a benzyl group), for example, an alkyl group having 1 to 12 carbon atoms which may have a substituent].
  • quaternary ammonium carboxylate examples include tetraethylammonium (meth)acrylate, tetrabutylammonium (meth)acrylate, benzyltributylammonium (meth)acrylate, tetraethylammonium aliphatic carboxylate, tetrabutylammonium aliphatic carboxylate, and benzyltributylammonium aliphatic carboxylate.
  • the basic catalyst may be ammonium betaine.
  • ammonium betaine include trimethylglycine, triethylglycine, tributylglycine, N-lauryl-N,N-dimethylglycine, N-(meth)acryloyloxyethyl-N,N-dimethylammonium- ⁇ -N-methylcarboxybetaine, and vinyl copolymers containing N-(meth)acryloyloxyethyl-N,N-dimethylammonium- ⁇ -N-methylcarboxybetaine.
  • the mixture containing a hydroxycarboxylic acid and/or its polymer and a basic catalyst further contains a carboxylic acid anhydride.
  • the carboxylic acid anhydride is not an essential component and may or may not be contained in the mixture.
  • a carboxylic acid anhydride is a compound formed by dehydration condensation of two carboxylic acids, and is a compound represented by the general formula: R b -CO-O-CO-R b ' [R b and R b ' each independently represent a monovalent organic group].
  • R b -CO-O-CO-R b ' [R b and R b ' each independently represent a monovalent organic group].
  • the carboxylic acid anhydride is not particularly limited, and examples thereof include (meth)acrylic acid anhydride, acetic acid anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, and benzoic acid anhydride.
  • one type of carboxylic acid anhydride may be used, or two or more types of carboxylic acid anhydrides may be used.
  • it is preferable to use (meth)acrylic acid anhydride it is preferable to use (meth)acrylic acid anhydride, and it is more preferable to use (meth)acrylic acid anhydride having the structure described below.
  • the (meth)acrylic anhydride is preferably a compound obtained by dehydration condensation of two compounds having a (meth)acrylic acid skeleton and a carboxylic acid skeleton.
  • the (meth)acrylic acid compound is represented by the formula (I): [In formula (I), R 1 to R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]
  • the (meth)acrylic anhydride represented by formula (I) is also referred to as "(meth)acrylic anhydride (I)".
  • R 1 to R 3 in formula (I) each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. It is preferable that R 1 to R 3 have a structure corresponding to the acrylic acid compound to be produced, from the viewpoints of isolability of the obtained acrylic acid compound and reduction of impurities that may be contained in the compound.
  • R 1 and R 2 in formula (I) are preferably the same as R 4 and R 5 in formula (III), respectively, and R 3 in formula (I) is preferably the same as R 6 in formula (III).
  • R 1 to R 3 each independently preferably represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably represent a hydrogen atom or a methyl group, and even more preferably represent a hydrogen atom.
  • R2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R1 and R3 represent a hydrogen atom.
  • R2 preferably represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
  • the mixture containing the hydroxycarboxylic acid and/or its polymer and the basic catalyst may contain one or more other components, such as additives such as a polymerization inhibitor, a solvent, etc.
  • Polymerization inhibitors are not particularly limited, but examples of phenolic compounds include hydroquinone, p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), etc., and examples of nitrogen-containing compounds include nitroxides such as piperidine-1-oxyl, pyrrolidine-1-oxyl, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, and 2,2,6,6-tetramethylpiperidine-1-oxyl, phenothiazine, 3,7-dioctyl ...
  • phenothiazine derivatives such as phenothiazine and 3,7-di-t-butylphenothiazine, and transition metal salts
  • copper salts such as copper dialkyldithiocarbamate (wherein the alkyl group is any of methyl, ethyl, propyl, and butyl groups and may be the same or different), copper acetate, copper salicylate, copper thiocyanate, copper nitrate, copper chloride, copper carbonate, copper hydroxide, and copper acrylate;
  • manganese dialkyldithiocarbamate wherein the alkyl group is any of methyl, ethyl, propyl, and butyl groups and may be the same or different
  • manganese diphenyldithiocarbamate manganese formate, manganese acetate, manganese octanoate, manganese naphthenate, manganese permanganate, and manganese salt of ethylene
  • polymerization inhibitor When a polymerization inhibitor is used, one type of polymerization inhibitor may be used, or two or more types may be used in combination.
  • the mixture contains a polymerization inhibitor, the polymerization of the (meth)acrylic acid compound generated in the reaction step can be suppressed, which is preferable since it is possible to improve the production efficiency of the (meth)acrylic acid compound. In addition, it is also possible to suppress the polymerization of by-products that may be generated.
  • the polymerization inhibitor is preferably a nitroxide such as piperidine-1-oxyl, pyrrolidine-1-oxyl, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, or 2,2,6,6-tetramethylpiperidine-1-oxyl, or a phenothiazine derivative such as phenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, or 3,7-di-t-butylphenothiazine, and more preferably 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl or 2,2,6,6-tetramethylpiperidine-1-oxyl.
  • a nitroxide such as piperidine-1-oxyl, pyrrolidine-1-oxyl, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, or 2,2,6,6-tetramethylpiperidine-1-oxyl
  • the content of the polymerization inhibitor is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 2 parts by mass, and even more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the polymer of 3-hydroxycarboxylic acid.
  • the amount of the polymerization inhibitor is equal to or greater than the above lower limit, the polymerization inhibitor effect of the (meth)acrylic acid compound can be enhanced.
  • the mixture in the production method of the present invention may or may not contain a solvent.
  • a solvent that may be contained in the mixture an aprotic organic solvent is preferable from the viewpoint of being less likely to inhibit the production of the (meth)acrylic acid compound.
  • examples of such an aprotic organic solvent include ethyl acetate, tetrahydrofuran, toluene, methyl ethyl ketone, and cyclopentanone.
  • the content of the solvent in the mixture is not particularly limited, and may be, for example, 0 to 80% by mass based on the total amount of the mixture.
  • the content of the solvent contained in the mixture is preferably 0 to 50 mass %, more preferably 0 to 30 mass %, even more preferably 0 to 20 mass %, even more preferably 0 to 10 mass %, and particularly preferably 0 to 5 mass %, based on the total amount of the mixture.
  • the amount of the basic catalyst per 100 parts by mass of the hydroxycarboxylic acid and its polymer is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, from the viewpoint of improving the yield of the (meth)acrylic acid compound.
  • the amount of the carboxylic acid anhydride represented by formula (I) relative to a total of 100 parts by mass of the hydroxycarboxylic acid and its polymer is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, from the viewpoint of improving the yield of the (meth)acrylic acid compound.
  • the amount of the carboxylic acid anhydride represented by formula (I) relative to the total amount of the hydroxycarboxylic acid and its polymer is preferably 0.05 to 25 mol %, more preferably 0.5 to 15 mol %, and even more preferably 2.5 to 10 mol %, from the viewpoint of improving the yield of the (meth)acrylic acid compound.
  • the production method of the present invention includes at least a reaction step of heating a mixture containing a hydroxycarboxylic acid and/or a polymer thereof with a basic catalyst to react with each other to produce a (meth)acrylic acid compound, (1) the mixture further comprises a carboxylic acid anhydride; and/or (2) A production method in which the weight average molecular weight of a polymer of a hydroxycarboxylic acid contained in the raw material is 10,000 or more.
  • the (meth)acrylic acid compound produced by the production method of the present invention is not particularly limited as long as it is a compound having a (meth)acrylic acid skeleton, and may be acrylic acid, methacrylic acid, and compounds in which at least one hydrogen atom of these is substituted with an alkyl group having 1 to 3 carbon atoms, as well as derivatives thereof (e.g., salts and esters).
  • the (meth)acrylic acid compound produced by the production method of the present invention usually has a structure corresponding to the polymer of the hydroxycarboxylic acid used as the raw material.
  • the hydroxycarboxylic acid and its polymer are represented by the formula (III)-1: [In formula (III)-1, R 4 to R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 or more]
  • the formula (III)-2 [In formula (III)-2, R 10 and R 11 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 or more]
  • the (meth)acrylic acid compound obtained by the production method of the present invention is represented by the formula (IV): [In formula (IV), R 7 to R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms] It is believed that the compound is represented by the formula (IV).
  • the (meth)acrylic acid compound obtained by the production method of the present invention may be one type of (meth)acrylic acid compound or a mixture of two or more types of (meth)acrylic acid compounds.
  • the reaction mechanism of the production method of the present invention is not limited in any way as long as it includes the above reaction steps, but it is believed that the reaction steps proceed according to the following reaction mechanism, for example.
  • the reaction steps proceed according to the following reaction mechanism, for example.
  • (1) when the mixture further includes a carboxylic acid anhydride we will explain (1) when the mixture further includes a carboxylic acid anhydride.
  • the hydroxycarboxylic acid is 3-hydroxypropionic acid, which is a type of 3-hydroxycarboxylic acid
  • the basic catalyst is sodium acrylate
  • the carboxylic anhydride is acrylic anhydride; however, this does not mean that the components are limited to these, and the mechanism is similarly applicable to other 3-hydroxycarboxylic acids and/or their polymers, other basic catalysts, and other carboxylic anhydrides.
  • the production method of the present invention is in no way limited to the following reaction mechanism.
  • ANa is sodium acrylate
  • (3HP) n is 3-hydroxypropionic acid or its polymer
  • AA is acrylic anhydride
  • AC is acrylic acid.
  • the negative charge A- of ANa acts on the proton of the terminal hydroxyl group of (3HP) n
  • the negative charge generated on the oxygen atom of (3HP) n attacks the carbonyl carbon of AA, resulting in AC1, ANa, and A-(3HP) n shown in (2).
  • the chemical formula of (3HP) n is shown as 3HP-(3HP) n-1 .
  • the negative charge A- of ANa acts on A-(3HP) n , resulting in AC2, ANa, and A-(3HP) n-1 shown in (3).
  • the negative charge A - of ANa acts on A-(3HP) n-1 , similar to the reaction shown in (2), to produce AC3, ANa, and A-(3HP) n-2 .
  • the n of (3HP) n decreases by one, and acrylic acid is produced sequentially.
  • the basic compound (e.g., AN a ) reacted in (1) may be a catalytic amount, and AN a reacted in (2) and (3) is sequentially generated in the system. Therefore, the basic compound used in the production method of the present invention is not particularly limited as long as it is a basic compound that acts on the proton of the terminal hydroxyl group of (3HP) n , and it is understood that those having various reactivities may be used.
  • the (meth)acrylic anhydride may be, for example, a compound represented by formula (I), and its structure is not particularly limited, but it is understood that by using a (meth)acrylic anhydride corresponding to the polymer of the 3-hydroxycarboxylic acid used, the acrylic acid compound obtained as the product can be a single compound, and impurities can be further reduced.
  • the hydroxycarboxylic acid is 2-hydroxyisobutyric acid, which is a type of 2-hydroxycarboxylic acid
  • the basic catalyst is sodium methacrylate
  • the carboxylic anhydride is methacrylic anhydride.
  • MANa is sodium methacrylate
  • (2HIB) n is 2-hydroxyisobutyric acid or its polymer
  • MAMA is methacrylic anhydride
  • MAC methacrylic acid.
  • the negative charge MA- of MANa acts on the proton of the terminal hydroxyl group of (2HIB) n
  • the negative charge generated on the oxygen atom of (2HIB) n attacks the carbonyl carbon of MAMA, producing MAC1, MANa, and MA-(2HIB) n shown in (5).
  • the chemical formula of (2HIB) n is shown as 2HIB-(2HIB) n-1 .
  • the negative charge MA- of MANa acts on MA-(2HIB) n , producing MAC2, MANa, and MA-(2HIB) n-1 shown in (6).
  • the negative charge MA - of MANa acts on MA-(2HIB) n-1 , similar to the reaction shown in (5), to generate MAC3, MANa, and MA-(2HIB) n-2 .
  • the n of (2HIB) n decreases by one, and methacrylic acid is sequentially generated.
  • the residues as major and minor components will be 1/10 of the polymer of 3-hydroxycarboxylic acid having a weight-average molecular weight of 1,000, and it is believed that the yield of acrylic acid will increase. That is, the lower the molecular weight, the more residues there are as major and minor components, and the lower the yield of acrylic acid. If there is a lot of water, the polymer shown in formula (1) is hydrolyzed, the weight average molecular weight decreases, and the molecular weight decreases, which is thought to increase the residues as major and minor components and reduce the yield.
  • the water content in the mixture containing a hydroxycarboxylic acid and/or a polymer thereof and a basic catalyst is preferably low.
  • the water content is preferably 0 to 15 mass %, more preferably 0 to 10 mass %, and even more preferably 0 to 5 mass %, based on the total amount of the mixture.
  • the amount of water contained in the (meth)acrylic acid compound product obtained can be reduced, and the handleability of the product is improved.
  • the amount of water contained in the (meth)acrylic acid compound product is preferably 0.1% by mass or less based on the total amount of the (meth)acrylic acid compound.
  • the weight-average molecular weight of the hydroxycarboxylic acid polymer contained in the raw material is 10,000 or more, it is considered that when the amount of water is equal to or less than the above upper limit, the residues as major and minor components in the above reaction scheme can be further reduced.
  • the manufacturing method of the present invention includes at least a reaction step in which a mixture containing at least a hydroxycarboxylic acid and/or its polymer with a basic catalyst is heated to react with the mixture to produce a (meth)acrylic acid compound.
  • the reaction step may be carried out, for example, by heating the mixture placed in a reaction vessel.
  • the reaction step may be carried out in a batch or continuous manner. Since the (meth)acrylic acid produced in the reaction step is prone to polymerization, it is preferable to carry out a step of distilling off the (meth)acrylic acid compound produced in the reaction step from the viewpoint of preventing such polymerization and improving the yield of the reaction product. For example, it is more preferable to carry out the reaction step and the distillation step of the produced (meth)acrylic acid simultaneously.
  • reaction apparatus examples include a reactor equipped with a stirrer, and a reaction apparatus configured to be capable of both heating the mixture and distilling off the produced (meth)acrylic acid (for example, an apparatus equipped with a thin film distiller or a Kugelrohr).
  • the heating conditions are not particularly limited as long as the hydroxycarboxylic acid and/or its polymer reacts with the basic catalyst, preferably together with the carboxylic anhydride, to produce a (meth)acrylic acid compound, but from the viewpoint of reaction efficiency, the heating temperature is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, and even more preferably 90°C or higher. From the viewpoint of easily suppressing unnecessary side reactions, the heating temperature may be preferably less than 300°C, more preferably 250°C or lower, even more preferably 220°C or lower, even more preferably 200°C or lower, particularly preferably 180°C or lower, particularly preferably 160°C or lower, and extremely preferably 140°C or lower.
  • the heating temperature in the reaction step may preferably be in the range of 50 to 300°C, 70 to 250°C, 80 to 220°C, 80 to 200°C, 80 to 180°C, 90 to 160°C, 90 to 140°C, etc.
  • the heating temperature in the reaction step is preferably 80 to 220°C, more preferably 80 to 200°C, even more preferably 80 to 180°C, even more preferably 90 to 160°C, and particularly preferably 90 to 140°C.
  • the heating time is not particularly limited and may be adjusted as appropriate depending on the progress of the reaction.
  • the reaction process can be carried out continuously by adding the raw material hydroxycarboxylic acid and/or its polymer to the reaction system while heating, and removing the generated (meth)acrylic acid compound from the reaction system.
  • a carboxylic acid anhydride it is preferable to also add the carboxylic acid anhydride, which is thought to be consumed by the reaction, to the reaction system.
  • the heating time is also not particularly limited.
  • the production method of the present invention further includes a step of distilling off the (meth)acrylic acid compound produced in the reaction step.
  • a step of distilling off the (meth)acrylic acid compound produced in the reaction step By distilling off the produced (meth)acrylic acid compound from the reaction system, it becomes possible to shift the equilibrium of the reaction in the direction of producing the (meth)acrylic acid compound, and as a result, the yield of the (meth)acrylic acid compound can be improved.
  • the step of distilling off the (meth)acrylic acid compound is carried out simultaneously with the reaction step.
  • Methods for distilling off the (meth)acrylic acid compound include distillation, particularly reduced pressure distillation.
  • the pressure in the system during reduced pressure distillation (degree of reduced pressure) is preferably lower than the vapor pressure of the resulting (meth)acrylic acid compound. Therefore, the upper limit of the degree of reduced pressure is preferably 101 kPa or less, more preferably 67 kPa or less, and even more preferably 40 kPa or less.
  • the lower limit of the degree of reduced pressure is preferably 1.3 kPa or more, preferably 6.7 kPa or more, more preferably 11 kPa or more, and even more preferably 16 kPa or more.
  • the manufacturing method of the present invention can produce a (meth)acrylic acid compound with few impurities.
  • the (meth)acrylic acid compound produced by the manufacturing method of the present invention has a low content of by-products such as water and propionic acid.
  • the manufacturing method of the present invention can provide a novel method for manufacturing a (meth)acrylic acid compound.
  • the (meth)acrylic acid compound manufactured by the manufacturing method of the present invention has a low impurity content and can be used as a useful raw material in the manufacture of resins such as poly(meth)acrylic acid.
  • HPLC HPLC measurement conditions were as follows: column; YMC-pack ODS-AM-302 150 mm ⁇ ⁇ 4.6 mm S-5 ⁇ m 120 A, temperature 40° C., flow rate 1 mL/min, detection wavelength 210 nm, mobile phase; acetonitrile/0.5 wt % phosphoric acid aqueous solution (ratio 1/1), analysis time: 25 minutes.
  • GC GC measurement conditions
  • column capillary column 007-1701, length 25 m, inner diameter 0.32 mm, liquid phase film thickness 1 ⁇ m (Quadex Corporation); column temperature; 50° C. (3 min) ⁇ temperature rise 10° C./min ⁇ 100° C. (0 min) ⁇ temperature rise 15° C./min ⁇ 250° C. (15 min); injection temperature; 220° C.; detector (FID) temperature: 220° C.; carrier gas; He; flow rate; 2.23 mL/min (inlet pressure 85.0 kPa); split ratio: 50.0; analysis time 25 min.
  • GPC GPC measurement conditions were as follows: column: TSK-gel SuperAWH-H (4 columns) (manufactured by Tosoh Corporation), mobile phase: N,N-dimethylformamide (0.03 M lithium bromide solution), thermostatic bath: 40° C., flow rate: 0.6 mL/min, analysis time: 30 min. Mw is a value converted into standard polystyrene.
  • raw material (B) was calculated from the HPLC area ratio in the same manner as for raw material (A) above, and the result was that it was a 6.5-mer, while raw material (B) was a 7-mer with a weight average molecular weight of 522.
  • the filtrate obtained when filtering out the raw material (F) was measured by GPC under the same conditions as above, and the Mw was 643,000. Therefore, it is considered that the Mw of the obtained solid p-3HP is at least 643,000 or more. In addition, from this result, it is considered that the raw material (F) is at least an 8,922-mer.
  • ⁇ Measurement conditions Measuring equipment: Heating conditions: 50°C to 100°C; 10°C/min, 100°C; 5 min, 100°C to 400°C; 10°C/min ⁇ Measurement results> Raw material (A): 165°C Raw material (B): 175°C Raw material (C): 232°C Raw material (D): 237°C Raw material (E): 243°C Raw material (F): 266°C
  • Example 1 240 mg of the raw material (A) containing 3-HPA and its polymer obtained in Production Example 1, 5.7 mg of potassium acrylate (manufactured by Nippon Shokubai Co., Ltd.), 50.3 mg of acrylic anhydride (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 0.3 mg of a polymerization inhibitor (commercially available 4-hydroxy-TEMPO) were placed in a 10 mL pressure-resistant container and heated at 100° C. for 1 hour while stirring to obtain 296 mg of reaction product (1).
  • potassium acrylate manufactured by Nippon Shokubai Co., Ltd.
  • acrylic anhydride manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • a polymerization inhibitor commercially available 4-hydroxy-TEMPO
  • the obtained reaction product (1) was analyzed by HPLC, and the amounts of (a) acrylic acid, (b) A-3-HPA polymer, (c) 3-HPA polymer, and (d) 3-HPA, which are represented by the following chemical formulas, contained in the reaction product (1) were quantified.
  • acrylic acid manufactured by Tokyo Kaseihin Kogyo Co., Ltd.
  • the quantitative results are shown in Table 1, and the HPLC chart is shown in FIG. 2.
  • Example 2 A reaction product (2) according to Example 2 was produced in the same manner as in Example 1, except that after heating at 100° C. for 1 hour, heating was further carried out at 150° C. for 1 hour. The results are shown in Table 1.
  • Example 3 1000 mg of the raw material (A) obtained in Production Example 1, 24 mg of potassium acrylate (pKa of acrylic acid 4.26), 200 mg of acrylic anhydride, and 1 mg of a polymerization inhibitor (4-hydroxy-TEMPO) were charged into a Kugelrohr sample ball, and while rotating, the vacuum degree was set to 25 KPa to 18 KPa, the jacket temperature was set to 125 ° C, and the mixture was heated to 125 ° C. Then, the mixture was heated while increasing the temperature from that temperature to 194 ° C. in 2 hours, thereby obtaining a transparent distillate. When this distillate was analyzed by HPLC and 1 H-NMR, the distillate contained 620 mg of acrylic acid (GC content 96.6%).
  • Example 4 A distillate and a reaction product (4) were obtained and analyzed in the same manner as in Example 3, except that the pressure was changed from 20 KPa to 18 KPa and other conditions and compositions were changed to those shown in Table 1. The analysis results are shown in Table 1.
  • Comparative Examples 1 to 3 The production of acrylic acid and the analysis of comparative reaction products (1) to (3) were carried out in the same manner as in Example 1, except that the conditions were changed as shown in Table 1. The results are shown in Table 1.
  • the weight loss rate during the reaction under the following conditions was measured using a TG-DTA device and corresponds to the yield.
  • Example 5 100 parts by mass of raw material (B) containing 3-HPA and its polymer obtained in Production Example 2, 2 parts by mass of potassium acrylate (manufactured by Nippon Shokubai Co., Ltd.), and 22 parts by mass of acrylic anhydride (manufactured by Osaka Organic Chemical Industry Co., Ltd.) were placed in an aluminum container in an amount of 10 mg, heated from 50°C to 100°C over 5 minutes, then maintained at 100°C for 5 minutes, heated to 150°C over 5 minutes, and heated at 150°C for 55 minutes (heating condition 1). The heating time from 50 to 150°C was 70 minutes in total. From the weight reduction rate, the yield corresponds to 66.1%.
  • Example 6-1 The reaction was carried out in the same manner as in Example 5, except that the raw material (B) was replaced with the raw material (C) (Mw: 20,700) containing 3-HPA and its polymer obtained in Production Example 3, and acrylic anhydride was not used. From the weight reduction rate, the yield was equivalent to 22.4%.
  • Example 6-2 The reaction was carried out in the same manner as in Example 6-1, except that 5 parts by mass of acrylic anhydride was further used. Based on the weight loss rate, the yield was equivalent to 56.0%.
  • Example 6-3 The reaction was carried out in the same manner as in Example 6-2, except that the amount of acrylic anhydride was changed to 10 parts by mass. Based on the weight reduction rate, the yield was equivalent to 85.5%.
  • Example 6-4 The reaction was carried out in the same manner as in Example 6-2, except that the amount of acrylic anhydride was changed to 25 parts by mass. Based on the weight reduction rate, the yield was equivalent to 95.5%.
  • Example 6-5 The reaction was carried out in the same manner as in Example 6-1, except that sodium 3-hydroxypropionate (manufactured by Cosmo Bio Co., Ltd.) was used instead of potassium acrylate. Based on the weight loss rate, the yield was equivalent to 10.2%.
  • Example 6-6 A reaction was carried out in the same manner as in Example 6-1, except that 2 parts by mass of potassium acrylate and 2 parts by mass of sodium 3-hydroxypropionate (manufactured by Cosmo Bio Co., Ltd.) were used. Based on the weight reduction rate, the yield was equivalent to 35.0%.
  • Examples 6-7 The reaction was carried out in the same manner as in Example 6-6, except that 9 parts by mass of acrylic anhydride was further used. Based on the weight loss rate, the yield was equivalent to 54.0%.
  • Example 6 to 8 The reaction was carried out in the same manner as in Example 6-1, except that the amount of potassium acrylate was changed to 6 parts by mass. Based on the weight reduction rate, the yield was equivalent to 65.7%.
  • Example 6 to 9 The reaction was carried out in the same manner as in Example 6-1, except that 5 parts by mass of potassium carbonate (K carbonate) was used instead of potassium acrylate. Based on the weight loss rate, the yield was equivalent to 65.0%.
  • K carbonate potassium carbonate
  • Comparative Example 5 The reaction was carried out in the same manner as in Example 5, except that only 100 parts by mass of the raw material (B) containing 3-HPA and its polymer obtained in Production Example 2 was used. Based on the weight loss rate, the yield was equivalent to 0.6%.
  • Comparative Example 6 The reaction was carried out in the same manner as in Comparative Example 5, except that the raw material (B) was replaced with only the raw material (C) containing 3-HPA and its polymer obtained in Production Example 3. From the weight reduction rate, the yield was equivalent to 0.6%.
  • Example 7-1 The reaction was carried out in the same manner as in Example 5, except that the raw material (B) was replaced with the raw material (D) (Mw: 74,600) containing 3-HPA and a polymer thereof obtained in Production Example 4, the amount of potassium acrylate was 5 parts by mass, and acrylic anhydride was not used. Based on the weight reduction rate, the yield was equivalent to 41.0%.
  • Example 7-2a The reaction was carried out in the same manner as in Example 7-1, except that 10 parts by mass of acrylic anhydride was further used. Based on the weight reduction rate, the yield was equivalent to 87.8%.
  • Example 7-2b The reaction product 7-2b was obtained in the same manner as in Example 7-2a, except that, instead of heating condition 1, the mixture placed in a pressure-resistant container was heated with stirring, heated from 50°C to 100°C over 5 minutes, then maintained at 100°C for 5 minutes, then heated to 150°C over 5 minutes, and heated at 150°C for 85 minutes (heating condition 2). The heating time from 50 to 150°C under heating condition 2 was 85 minutes in total. From the weight loss, the yield was equivalent to 97.2%.
  • Example 7-2c The reaction product 7-2c was obtained in the same manner as in Example 7-2a, except that, instead of heating condition 1, the mixture placed in a pressure-resistant container was heated with stirring, heated from 50°C to 100°C over 5 minutes, then maintained at 100°C for 5 minutes, then heated to 150°C over 5 minutes, and heated at 150°C for 135 minutes (heating condition 3). The heating time from 50 to 150°C under heating condition 3 was 150 minutes in total. From the weight loss, the yield was equivalent to 98.3%.
  • Example 7-3a to 7-3c Analyses were carried out in the same manner as in Examples 7-2a to 7-2c, except that 5 parts by mass of potassium carbonate was used instead of potassium acrylate, and acrylic anhydride was not used. From the weight reduction rate, the yield of 7-3a was 55.7%, the yield of 7-3b was 71.4%, and the yield of 7-3a was 80.9%, respectively.
  • Example 8-1 The reaction was carried out in the same manner as in Example 5, except that the raw material (B) was replaced with the raw material (E) (Mw: 139,700) containing 3-HPA and a polymer thereof obtained in Production Example 5, the amount of potassium acrylate was 5 parts by mass, and acrylic anhydride was not used. From the weight reduction rate, the yield was equivalent to 48.3%.
  • Example 8-2a The reaction was carried out in the same manner as in Example 8-1, except that 10 parts by mass of acrylic anhydride was further used. Based on the weight reduction rate, the yield was equivalent to 91.0%.
  • Example 8-2b The reaction was carried out in the same manner as in Example 8-2a, except that heating was carried out under heating condition 2 instead of heating condition 1. From the weight reduction rate, the yield corresponds to 97.2%.
  • Example 8-2c The reaction was carried out in the same manner as in Example 8-2a, except that heating was carried out under heating condition 3 instead of heating condition 1. The yield was equivalent to 97.2% based on the weight reduction rate.
  • Examples 8-3a to 8-3b The reactions were carried out in the same manner as in Examples 8-2a to 8-2c, except that 5 parts by mass of potassium carbonate was used instead of potassium acrylate, and acrylic anhydride was not used. From the weight reduction rates, the yield of 8-3a was 59.9%, the yield of 8-3b was 89.3%, and the yield of 8-3c was 97.7%, respectively.
  • Example 9-1 The reaction was carried out in the same manner as in Example 5, except that the raw material (B) was replaced with the raw material (F) (Mw: at least 643,000) containing 3-HPA and its polymer obtained in Production Example 5, the amount of potassium acrylate was 5 parts by mass, and acrylic anhydride was not used. From the weight reduction rate, the yield was equivalent to 34.7%.
  • Example 9-2a to 9-2c The reaction was carried out in the same manner as in Example 9-1, except that 11 parts by mass of acrylic anhydride were further used. From the weight reduction rate, the yield of acrylic acid in 9-2a was equivalent to 50.2%. In addition, the reaction was carried out in the same manner as above, except that heating condition 1 was changed to heating condition 2. From the weight reduction rate, the yield of acrylic acid in 9-2b was equivalent to 77.3%. In addition, analysis was carried out in the same manner as above, except that heating condition 1 was changed to heating condition 3. From the weight reduction rate, the yield of acrylic acid in 9-2c was equivalent to 98.2%.
  • Example 9-3a to 9-3c The reaction was carried out in the same manner as in Examples 9-2a to 9-2c, except that the amount of acrylic anhydride was changed to 10 parts by mass and zinc (II) acrylate was used instead of potassium acrylate. From the weight reduction rate, the yield of 9-3a was 46.0%, the yield of 9-3b was 77.4%, and the yield of 9-3c was 95.1%, respectively.
  • Example 9-4a to 9-4c Except for using potassium carbonate instead of potassium acrylate, the reactions were carried out under heating conditions 1 to 3 in the same manner as in Example 9-1. From the weight reduction rates, the yields of 9-4a, 9-4b, and 9-4c corresponded to 67.2%, 92.4%, and 96.6%, respectively.
  • Example 9-5a to 9-5c Except for using sodium carbonate instead of potassium acrylate, the reactions were carried out under heating conditions 1 to 3 in the same manner as in Example 9-1. From the weight reduction rates, the yields of 9-5a, 9-5b, and 9-5c corresponded to 41.0%, 68.3%, and 93.5%, respectively.
  • Example 9-6a to 9-6c The reactions were carried out in the same manner as in Examples 9-5a to 9-5c, except that 20 parts by mass of water was added. From the weight reduction rate, the yield of 9-6a was 33.8%, the yield of 9-6b was 58.8%, and the yield of 9-6c was 76.3%, respectively.
  • Example 10 0.500 g of raw material (F) and 0.025 g of potassium carbonate were mixed in a container and set in a vacuum distiller. When the mixture was heated for about 140 minutes under conditions of a bath temperature of 100 to 155°C and an internal pressure of 20.6 to 16.0 kPa, gas thought to be carbon dioxide gas was generated in the early stages. After that, 0.470 g of a fraction was obtained. When the fraction obtained was analyzed by GC, it was found to contain 97.0% acrylic acid, and the yield was 94%.
  • Tables 2 and 3 confirm that the production method of the present invention described in Examples 5 to 9 allows the reaction to proceed even at a relatively low temperature of about 150°C, and produces acrylic acid.
  • acrylic acid could be obtained regardless of the molecular weight of the raw material.
  • the weight-average molecular weight of the polymer of 3-hydroxycarboxylic acid contained in the raw material is 10,000 or more, acrylic acid could be obtained even when no carboxylic acid anhydride was further contained.
  • Example 9-5 in which the mixture contains less water, had a higher yield of the desired product, acrylic acid, than Example 9-6, in which the mixture contains water.
  • Example 9-5c and Example 10 which have the same types and ratios of raw materials and basic catalysts, it was confirmed that the weight loss rate in Example 9-5 and the yield of acrylic acid measured by GC analysis in Example 10 were almost the same. Therefore, it can be said that the weight loss rate in each of the above examples corresponds to the yield.

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WO2025178108A1 (ja) * 2024-02-20 2025-08-28 株式会社日本触媒 （メタ）アクリル酸の製造方法

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US3487101A (en) * 1963-09-17 1969-12-30 Lonza Ag Preparation of methacrylic compounds by dehydration of alpha - hydroxybutyric acid compounds
WO2010071019A1 (ja) * 2008-12-17 2010-06-24 国立大学法人九州工業大学 ２－ヒドロキシイソ酪酸ポリマーの製造方法及び解重合方法
US20200377440A1 (en) * 2017-06-30 2020-12-03 Novomer, Inc. Compositions for Improved Production of Acrylic Acid
WO2023234688A1 (ko) * 2022-05-31 2023-12-07 주식회사 엘지화학 아크릴산 제조 방법

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WO2014002886A1 (ja) 2012-06-27 2014-01-03 株式会社日本触媒 （メタ）アクリル酸の製造方法、及び、親水性樹脂の製造方法
JP6193010B2 (ja) 2012-06-27 2017-09-06 株式会社日本触媒 （メタ）アクリル酸の製造方法、及び、親水性樹脂の製造方法
JP6193011B2 (ja) 2012-06-27 2017-09-06 株式会社日本触媒 （メタ）アクリル酸の製造方法、及び、親水性樹脂の製造方法

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Publication number Priority date Publication date Assignee Title
US3487101A (en) * 1963-09-17 1969-12-30 Lonza Ag Preparation of methacrylic compounds by dehydration of alpha - hydroxybutyric acid compounds
WO2010071019A1 (ja) * 2008-12-17 2010-06-24 国立大学法人九州工業大学 ２－ヒドロキシイソ酪酸ポリマーの製造方法及び解重合方法
US20200377440A1 (en) * 2017-06-30 2020-12-03 Novomer, Inc. Compositions for Improved Production of Acrylic Acid
WO2023234688A1 (ko) * 2022-05-31 2023-12-07 주식회사 엘지화학 아크릴산 제조 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025178108A1 (ja) * 2024-02-20 2025-08-28 株式会社日本触媒 （メタ）アクリル酸の製造方法

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