Classifications

• • 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
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
  • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/02—Monohydroxylic acyclic alcohols
  • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
  • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
  • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
  • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring

Definitions

• the present invention relates to a method for producing an ester compound, an ester compound, and a method for reducing the odor of an ester compound. Specifically, the present invention relates to a method for producing a bio-derived ester compound, which can obtain a bio-derived ester compound with reduced odor using a bio-derived raw material.
• ester compounds are used to create compositions with desired properties (e.g., Patent Documents 1 to 3).
• Known methods for producing such ester compounds include reacting a carboxylic acid with a monohydric alcohol, as described in Patent Documents 4 and 5.
• the object of the present invention is to provide a production method for a bio-derived ester compound that can obtain a bio-derived ester compound with reduced odor while using bio-derived raw materials.
• the present invention is a method for producing a bio-derived ester compound, comprising: a step of obtaining a bio-derived branched primary alcohol having a branched alkyl group having 6 to 12 carbon atoms, the step including dimerizing one or more selected from the group consisting of a bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms, a bio-derived linear primary alcohol having a linear alkenyl group having 3 to 6 carbon atoms, a bio-derived linear aldehyde having a linear alkyl group having 3 to 6 carbon atoms, and a bio-derived linear aldehyde having a linear alkenyl group having 3 to 6 carbon atoms; and a step of obtaining a bio-derived ester compound using the obtained bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound or an anhydride thereof having a hydrocarbon group having 1
• the present invention relates to a bio-derived ester compound produced by the above production method. Furthermore, in another embodiment, the present invention relates to a cosmetic or cleansing agent containing the above ester compound. In yet another embodiment, the present invention is a method for reducing the odor of an ester compound, comprising reacting a bio-derived branched primary alcohol having a branched alkyl group having 6 to 12 carbon atoms as a raw material.
• the present invention provides a method for producing a bio-derived ester compound that can obtain a bio-derived ester compound with reduced odor using a bio-derived raw material.
• the bio-derived linear primary alcohol used in the present invention is one or more selected from the group consisting of bio-derived linear primary alcohols having a linear alkyl group of 3 to 6 carbon atoms, which is obtained from plant resources, etc. (hereinafter, also referred to simply as "bio-derived”) and which have a structure in which one hydrogen atom bonded to one terminal carbon atom of a linear alkane having 3 to 6 carbon atoms is replaced with one hydroxyl group, and bio-derived linear primary alcohols having a linear alkenyl group of 3 to 6 carbon atoms, which are obtained from plant resources, etc.
• bio-derived linear primary alcohols having a linear alkyl group of 3 to 6 carbon atoms which is obtained from plant resources, etc.
• bio-derived linear primary alcohols having a linear alkyl group having 3 to 6 carbon atoms include bio-derived n-propanol (1-propanol), bio-derived n-butanol (1-butanol), bio-derived n-pentanol (1-pentanol), and bio-derived n-hexanol (1-hexanol).
• bio-derived linear primary alcohols having a linear alkenyl group having 3 to 6 carbon atoms include bio-derived n-propenyl alcohol (allyl alcohol), bio-derived n-butenyl alcohol (crotyl alcohol), bio-derived n-pentenyl alcohol, and bio-derived n-hexenyl alcohol.
• bio-derived linear primary alcohol a bio-derived linear primary alcohol obtained by a known method can be used.
• a bio-derived linear primary alcohol obtained by synthesis using various bio-derived compounds obtained from plant resources such as palm oil, palm kernel oil, soybean oil, rapeseed oil, castor oil, olive oil, cottonseed oil, coconut oil, corn oil, safflower oil, sesame oil, sunflower oil, camellia oil, and linseed oil, etc., can be used.
• the method of fermenting biomass derived from corn, sugar cane, sugar beet, banana, wheat, barley, rye, potato, sweet potato, cassava, taro, broad bean, lentil, pea, etc. with a microorganism to obtain a bio-derived linear primary alcohol is not particularly limited, and a known method can be used.
• a method can be used in which sugars such as cellulose obtained from biomass derived from corn, sugar cane, sugar beet, banana, wheat, barley, rye, potato, sweet potato, cassava, taro, broad bean, lentil, pea, etc. are fermented and/or metabolized by microorganisms such as fungi, enzymes, and yeasts that have the ability to ferment and/or metabolize under an environment of appropriate temperature, humidity, atmosphere, etc.
• the method for obtaining a bio-derived linear primary alcohol by synthesis using as a raw material various bio-derived compounds obtained from plant resources such as palm oil, palm kernel oil, soybean oil, rapeseed oil, olive oil, cottonseed oil, coconut oil, etc. is not particularly limited, and any known method can be used.
• a method in which fatty acid glycerides contained in vegetable oils such as palm oil, palm kernel oil, soybean oil, rapeseed oil, castor oil, olive oil, cottonseed oil, coconut oil, corn oil, safflower oil, sesame oil, sunflower oil, camellia oil, and linseed oil are hydrolyzed to obtain a fatty acid, which is then methyl esterified and then hydrogenated; a method in which a bio-derived linear aldehyde having a linear alkyl group with 3 to 6 carbon atoms or a bio-derived linear aldehyde having a linear alkenyl group with 3 to 6 carbon atoms is hydrogenated by a known method, etc. can be used.
• a bio-derived linear primary alcohol having a hydrocarbon group with a different number of carbon atoms from that of the bio-derived compound used as the raw material may be produced.
• a bio-derived alcohol such as ethanol or propanol may be oxidized or dehydrogenated by a known method to obtain an aldehyde compound, and the obtained aldehyde compound may then be condensed or hydrogenated to produce a bio-derived linear primary alcohol having a greater number of carbon atoms than that of the hydrocarbon group contained in the bio-derived alcohol used as the raw material.
• the bio-derived linear primary alcohol used in the present invention does not need to have all of its carbon atoms derived from biomolecules, but from the standpoint of environmental considerations and ease of production, it is preferable that 50% or more of the carbon atoms constituting the bio-derived linear primary alcohol are bio-derived carbon atoms, and it is even more preferable that all of the carbon atoms constituting the bio-derived linear primary alcohol are bio-derived carbon atoms.
• bio-derived linear primary alcohol used in the present invention one of the above-mentioned bio-derived linear primary alcohols or two or more of the above-mentioned bio-derived linear primary alcohols may be used, but from the viewpoint of ease of producing a single bio-derived ester compound, it is preferable to use only one bio-derived linear primary alcohol. Furthermore, in the present invention, from the viewpoint of obtaining a bio-derived ester compound with reduced odor, it is preferable to use bio-derived n-butanol (1-butanol) as the bio-derived linear primary alcohol, and it is more preferable to use only bio-derived n-butanol.
• the bio-derived straight-chain aldehyde used in the present invention is one or more selected from the group consisting of bio-derived straight-chain aldehydes obtained from plant resources, etc., having a straight-chain alkyl group having 3 to 6 carbon atoms, which has a structure in which one terminal methyl group of a straight-chain alkane having 3 to 6 carbon atoms is replaced with one aldehyde group, and bio-derived straight-chain aldehydes obtained from plant resources, etc., having a straight-chain alkenyl group having 3 to 6 carbon atoms, which has a structure in which one terminal methyl group of a straight-chain alkene having 3 to 6 carbon atoms is replaced with one aldehyde group.
• bio-derived linear aldehydes having a linear alkyl group having 3 to 6 carbon atoms include bio-derived n-propionaldehyde (propanal), bio-derived n-butylaldehyde (butanal), bio-derived n-valeraldehyde (pentanal), and bio-derived n-hexylaldehyde (hexanal).
• bio-derived linear aldehydes having a linear alkenyl group having 3 to 6 carbon atoms include bio-derived n-propenealdehyde (acrolein), bio-derived n-propylenealdehyde (butenal, crotonaldehyde), bio-derived n-butylenealdehyde (pentenal), and bio-derived n-pentenealdehyde (hexenal).
• a bio-derived straight-chain aldehyde can be a bio-derived straight-chain aldehyde obtained by a known method.
• a bio-derived straight-chain aldehyde obtained by fermenting and/or metabolizing biomass derived from corn, sugar cane, sugar beet, banana, wheat, barley, rye, potato, sweet potato, cassava, taro, broad bean, lentil, pea, etc., by a microorganism a bio-derived straight-chain aldehyde obtained by synthesis using various bio-derived compounds obtained from plant resources such as palm oil, palm kernel oil, soybean oil, rapeseed oil, castor oil, olive oil, cottonseed oil, coconut oil, corn oil, safflower oil, sesame oil, sunflower oil, camellia oil, linseed oil, etc., as a raw material, or the like can be used.
• the method of obtaining a bio-derived linear aldehyde by fermenting biomass derived from corn, sugar cane, sugar beet, banana, wheat, barley, rye, potato, sweet potato, cassava, taro, broad bean, lentil, pea, etc., with a microorganism is not particularly limited, and a known method can be used.
• a method can be used in which sugars such as cellulose obtained from biomass derived from corn, sugar cane, sugar beet, banana, wheat, barley, rye, potato, sweet potato, cassava, taro, broad bean, lentil, pea, etc. are fermented and/or metabolized by microorganisms such as fungi, enzymes, and yeasts that have fermentation and/or metabolism capabilities under an environment of appropriate temperature, humidity, atmosphere, etc.
• the method for synthesizing a bio-derived straight-chain aldehyde using various bio-derived compounds obtained from plant resources such as palm oil, palm kernel oil, soybean oil, rapeseed oil, olive oil, cottonseed oil, coconut oil, etc. as raw materials is not particularly limited, and any known method can be used.
• a bio-derived straight-chain aldehyde having a hydrocarbon group with a different number of carbon atoms from that of the bio-derived compound used as the raw material may be produced and used in the present invention.
• Examples of such methods include a method of oxidizing or dehydrogenating a bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms or a bio-derived linear primary alcohol having a linear alkenyl group having 3 to 6 carbon atoms obtained by a known method, a method of hydroformylating a bio-derived alkene having 2 to 5 carbon atoms, such as bio-derived ethylene, bio-derived propylene, bio-derived butylene, or bio-derived pentene, obtained by a known method, with carbon monoxide and hydrogen by the oxo method, and a method of producing an aldehyde with an increased number of carbon atoms by condensing an aldehyde having 2 to 4 carbon atoms obtained by oxidizing or dehydrogenating a bio-derived alcohol such as ethanol or propanol by a known method.
• the bio-derived linear aldehyde used in the present invention does not need to have all of its carbon atoms derived from biomolecules, but from the standpoint of environmental considerations and ease of production, it is preferable that 50% or more of the carbon atoms constituting the bio-derived linear aldehyde are bio-derived carbon atoms, and it is even more preferable that all of the carbon atoms constituting the bio-derived linear aldehyde are bio-derived carbon atoms.
• bio-derived linear aldehyde used in the present invention one of the above-mentioned bio-derived linear aldehydes or two or more of them may be used, but from the viewpoint of ease of producing a single bio-derived ester compound, it is preferable to use one bio-derived linear aldehyde. Furthermore, in the present invention, from the viewpoint of ease of obtaining a bio-derived ester compound with reduced odor, it is preferable to use bio-derived n-butylaldehyde (butanal) as the bio-derived linear aldehyde.
• the method for dimerizing one or more selected from the group consisting of bio-derived linear primary alcohols having a linear alkyl group with 3 to 6 carbon atoms, bio-derived linear primary alcohols having a linear alkenyl group with 3 to 6 carbon atoms, bio-derived linear aldehydes having a linear alkyl group with 3 to 6 carbon atoms, and bio-derived linear aldehydes having a linear alkenyl group with 3 to 6 carbon atoms is not particularly limited, and known methods can be used for each. For example, the method for dimerizing alcohols described in Catal. Sci. Technol., 2015, vol. 5, pp.
• a method can be used in which, by reacting and dimerizing two bio-derived linear primary alcohols having a linear alkyl group having 3 to 6 carbon atoms, two bio-derived linear primary alcohols having a linear alkenyl group having 3 to 6 carbon atoms, two bio-derived linear aldehydes having a linear alkyl group having 3 to 6 carbon atoms, or two bio-derived linear aldehydes having a linear alkenyl group having 3 to 6 carbon atoms, in the presence of a catalyst, a solvent, or the like as necessary, under a reduced pressure environment, a normal pressure environment, or a pressurized environment, at room temperature or with heating.
• a method may be used in which, in a system in which two or more types selected from the group consisting of a bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms, a bio-derived linear primary alcohol having a linear alkenyl group having 3 to 6 carbon atoms, a bio-derived linear aldehyde having a linear alkyl group having 3 to 6 carbon atoms, and a bio-derived linear aldehyde having a linear alkenyl group having 3 to 6 carbon atoms are mixed, the bio-derived linear primary alcohols and the bio-derived linear aldehydes are reacted with each other under the above conditions to dimerize the respective types.
• a method may be used in which the same bio-derived linear primary alcohols and the same bio-derived linear aldehydes are reacted with each other to dimerize the respective types.
• a bio-derived branched primary alcohol can be obtained by a process of dimerizing bio-derived propanols together, bio-derived n-butanols together, bio-derived n-pentanols together, or bio-derived n-hexanols together
• a bio-derived branched primary alcohol can be obtained by a process of dimerizing bio-derived n-propanols together, bio-derived n-butanal together, n-pentanals together, or n-hexanols together.
• the catalysts that can be used when dimerizing the bio-derived linear primary alcohol and when dimerizing the bio-derived linear aldehyde are not particularly limited, and known catalysts can be used depending on the purpose.
• catalysts include metal catalysts such as powders, oxides, complexes, salts, and alkoxides of metals such as copper, silver, zinc, nickel, palladium, platinum, cobalt, rhodium, iridium, iron, calcium, potassium, magnesium, ruthenium, manganese, chromium, and molybdenum, etc., nitroxyl radical catalysts such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), and basic compounds such as oxides, hydroxides, carbonates, carboxylates, phosphates, amine salts, and alkoxides of alkali metals such as lithium, sodium, and potassium, or alkaline earth metals such as magnesium and calcium, etc., and one or more of these can be used.
• a compound that serves as a ligand may be used in combination.
• ligands include olefin ligands such as ethylene, norbornene, norbornadiene, 1,7-octadiene, 1,5-cyclooctadiene, and pentamethylcyclopentadienyl; phosphine ligands such as ethylenebis(diphenylphosphine), cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, tri-t-butylphosphine, and triphenylphosphine; and nitrogen-containing ligands such as triethylamine, benzylamine, bipyridyl, bisiminopyridine, and imidazole.
• a basic compound that can be used as a catalyst the above-mentioned basic compound supported on zeolite, silica, alumina zirconia, magnesia, activated carbon, graphite, carbon nanotubes, etc. may be used.
• one or more catalysts selected from the group consisting of metal catalysts and basic compounds, more preferably one or more metal powders or oxides of copper, nickel, or palladium, and oxides, hydroxides, or phosphates of sodium, potassium, magnesium, or calcium, even more preferably one or more copper powder, copper oxide, and oxides or phosphates of potassium or calcium, and particularly preferably one or more copper powder, tripotassium phosphate, and calcium oxide.
• the amount of the catalyst when a catalyst is used when dimerizing the bio-derived linear primary alcohol and when dimerizing the bio-derived linear aldehyde, is not particularly limited and can be adjusted appropriately depending on the purpose, but from the viewpoint of carrying out the reaction efficiently, the amount of the catalyst used is preferably 0.001 to 50 parts by mass, more preferably 0.1 to 45 parts by mass, even more preferably 1 to 40 parts by mass, and particularly preferably 10 to 35 parts by mass, when the amount of the bio-derived linear primary alcohol and the bio-derived linear aldehyde used is taken as 100 parts by mass.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in the presence of a catalyst and a method of dimerizing two bio-derived linear aldehydes in the presence of a catalyst, respectively.
• the solvents that can be used when dimerizing the bio-derived linear primary alcohol and when dimerizing the bio-derived linear aldehyde are not particularly limited, and known solvents can be used depending on the purpose, such as water, pentane, hexane, heptane, octane, decane, dodecane, benzene, toluene, xylene, ethylbenzene, dodecylbenzene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diphenyl ether, dibenzyl ether, diallyl ether, tetrahydrofuran, dioxane, N-methyl-2-pyrrolidone, ethyl butyrate, butyl butyrate, ethyl acetate, butyl acetate, dimethylformamide, N,N-dimethylacetamide, acetonitrile, propionitrile, benzonitrile, etc.,
• the amount of the solvent when a solvent is used when dimerizing the bio-derived linear primary alcohol and when dimerizing the bio-derived linear aldehyde, is not particularly limited and can be adjusted appropriately depending on the purpose, but from the viewpoint of efficiently carrying out the reaction, the amount of the solvent used is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, and even more preferably 3 to 200 parts by mass, when the amount of the bio-derived linear primary alcohol and the bio-derived linear aldehyde used is taken as 100 parts by mass.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in the absence of a solvent and a method of dimerizing by reacting two bio-derived linear aldehydes in the absence of a solvent, respectively, and in particular in this case, it is more preferable to use a method of dimerizing by reacting the same bio-derived linear primary alcohols together or a method of dimerizing by reacting the same linear primary aldehydes together.
• the temperature when dimerizing the bio-derived linear primary alcohol and when dimerizing the bio-derived linear aldehyde is not particularly limited as long as it is a temperature at which the bio-derived linear primary alcohol or the bio-derived linear aldehyde can be dimerized, and can be appropriately adjusted depending on the purpose.
• the temperature can be from room temperature to 340°C, and among these, from the viewpoint of easily obtaining a bio-derived ester compound with reduced odor, it is preferably 60 to 330°C, more preferably 120 to 320°C, even more preferably 180 to 310°C, and particularly preferably 240 to 300°C.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in a heated environment and a method of dimerizing by reacting two bio-derived linear aldehydes in a heated environment, respectively, and in particular in this case, it is more preferable to use a method of dimerizing by reacting the same bio-derived linear primary alcohols together, or a method of dimerizing by reacting the same linear primary aldehydes together.
• the reaction times for dimerizing the bio-derived linear primary alcohol and for dimerizing the bio-derived linear aldehyde are not particularly limited and can be adjusted appropriately depending on the purpose.
• the reaction times can be 10 minutes to 72 hours, respectively.
• the pressure when at least one of the dimerization of the bio-derived linear primary alcohol and the dimerization of the bio-derived linear aldehyde is carried out in a reduced pressure environment, the pressure is not particularly limited and can be adjusted appropriately depending on the purpose, but can be carried out in a pressure environment of, for example, 0.01 Pa to 80,000 Pa. Furthermore, when at least one of the dimerization of the bio-derived linear primary alcohol and the dimerization of the bio-derived linear aldehyde is carried out in a pressurized environment, the pressure is not particularly limited and can be adjusted appropriately depending on the purpose, but can be carried out in an environment pressurized by, for example, 0.001 MPa to 10 MPa with atmospheric pressure as the standard.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols under normal pressure and a method of dimerizing by reacting two bio-derived linear aldehydes under normal pressure, respectively, and in particular in this case, it is more preferable to use a method of dimerizing by reacting the same bio-derived linear primary alcohols together, or a method of dimerizing by reacting the same linear primary aldehydes together.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in the presence of a catalyst and in the absence of a solvent, and a method of dimerizing by reacting two bio-derived linear aldehydes in the presence of a catalyst and in the absence of a solvent, respectively, and in particular in this case, a method of dimerizing by reacting the same bio-derived linear primary alcohols together, or a method of dimerizing by reacting the same linear primary aldehydes together is even more preferable.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in the presence of a catalyst under normal pressure, and a method of dimerizing by reacting two bio-derived linear aldehydes in the presence of a catalyst under normal pressure, respectively, and in particular in this case, a method of dimerizing by reacting the same bio-derived linear primary alcohols together, or a method of dimerizing by reacting the same linear primary aldehydes together is more preferable.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in a heated environment in the presence of a catalyst and by reacting two bio-derived linear aldehydes in a heated environment in the presence of a catalyst, respectively, and in this particular case, a method of dimerizing by reacting the same bio-derived linear primary alcohols together, or a method of dimerizing by reacting the same linear primary aldehydes together is even more preferable.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in the presence of a catalyst, in a heated environment, and in the absence of a solvent, and a method of dimerizing by reacting two bio-derived linear aldehydes in the presence of a catalyst, in a heated environment, and in the absence of a solvent, respectively.
• a method of dimerizing by reacting the same bio-derived linear primary alcohols together, or a method of dimerizing by reacting the same linear primary aldehydes together is particularly preferable.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in the presence of a catalyst, in a heated environment, and in a normal pressure environment, and a method of dimerizing by reacting two bio-derived linear aldehydes in the presence of a catalyst, in a heated environment, and in a normal pressure environment, respectively.
• a method of dimerizing by reacting the same bio-derived linear primary alcohols together, or a method of dimerizing by reacting the same linear primary aldehydes together is particularly preferable.
• the method of dimerizing by reacting two bio-derived linear primary alcohols and two bio-derived linear aldehydes is a method of dimerizing by reacting two bio-derived linear primary alcohols in the presence of a catalyst, in a heated environment, in the absence of a solvent, and in a normal pressure environment, and a method of dimerizing by reacting two bio-derived linear aldehydes in the presence of a catalyst, in a heated environment, in the absence of a solvent, and in a normal pressure environment, respectively, and in this case, a method of dimerizing by reacting the same bio-derived linear primary alcohols together, or a method of dimerizing by reacting the same linear primary aldehydes together is most preferable.
• the process for obtaining a bio-derived branched primary alcohol having 6 to 12 carbon atoms may include a step of dimerizing the bio-derived linear primary alcohol when a bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms is used as the raw material as the bio-derived linear primary alcohol, and may consist only of a step of dimerizing the bio-derived linear primary alcohol, or may include a purification step such as publicly known filtration, centrifugation, oil-water separation, decantation, distillation, deodorization, adsorption, etc.
• a bio-derived linear primary alcohol having a linear alkenyl group having 3 to 6 carbon atoms when used as the raw material as the bio-derived linear primary alcohol, it may include a step of dimerizing the bio-derived linear primary alcohol and a step of hydrogenating the obtained compound, and may further include a purification step such as publicly known filtration, centrifugation, oil-water separation, decantation, distillation, deodorization, adsorption, etc.
• the process may include a step of dimerizing the bio-derived linear aldehyde and a step of hydrogenating the obtained compound, and may further include a purification step using a known method such as filtration, centrifugation, oil-water separation, decantation, distillation, deodorization, or adsorption.
• the distillation method that can be used in the process of obtaining the bio-derived branched primary alcohol having 6 to 12 carbon atoms of the present invention is not particularly limited, and a known method can be appropriately selected depending on the purpose.
• methods such as normal pressure distillation, reduced pressure distillation, molecular distillation, and steam distillation can be used. More specifically, methods such as single distillation, fractional distillation, flash distillation, steam distillation, vacuum distillation, short path distillation, thin film distillation, reactive distillation, and extractive distillation can be used.
• the adsorption method that can be used in the process of obtaining the bio-derived branched primary alcohol having 6 to 12 carbon atoms of the present invention is not particularly limited, and for example, a method of adding an adsorbent such as activated clay, activated carbon, magnesium silicate, aluminum silicate, aluminum phosphosilicate, magnesium hydroxide, aluminum hydroxide, magnesium oxide, aluminum oxide, zeolite, or silica gel, stirring or leaving it as necessary, and then removing the adsorbent by a method such as filtration can be used.
• an adsorbent such as activated clay, activated carbon, magnesium silicate, aluminum silicate, aluminum phosphosilicate, magnesium hydroxide, aluminum hydroxide, magnesium oxide, aluminum oxide, zeolite, or silica gel
• the method for dimerizing the bio-derived linear primary alcohol among the above-mentioned methods, from the viewpoint of easily obtaining a bio-derived ester compound with reduced odor, it is preferable to use a method in which the bio-derived linear primary alcohols are dimerized by heating to 60 to 330°C in the presence of a catalyst as necessary and reacting for 10 minutes to 72 hours, and it is more preferable to use a method in which the bio-derived linear primary alcohols are dimerized by heating to 120 to 320°C in the presence of a catalyst and reacting for 30 minutes to 48 hours, and in particular, the same bio-derived linear primary alcohols are dimerized by heating to 120 to 320°C in the presence of a catalyst and reacting for 30 minutes to 48 hours.
• a method for dimerizing a bio-derived linear aldehyde among the above-mentioned methods, from the viewpoint of easily obtaining a bio-derived ester compound with reduced odor, it is preferable to use a method in which bio-derived linear aldehydes are dimerized by heating to 60 to 330°C in the presence of a catalyst as necessary and reacting for 10 minutes to 72 hours, and it is more preferable to use a method in which bio-derived linear aldehydes are dimerized by heating to 120 to 320°C in the presence of a catalyst and reacting for 30 minutes to 48 hours, in particular, between the same bio-derived linear primary aldehydes.
• bio-derived 2-methylpentanol can be obtained; when bio-derived n-butylaldehyde or bio-derived n-propylenealdehyde is used, bio-derived 2-ethylhexanol can be obtained; when bio-derived n-valeraldehyde or bio-derived n-butylenealdehyde is used, bio-derived 2-propylheptanol can be obtained; and when bio-derived n-hexylaldehyde or bio-derived n-pentenealdehyde is used, bio-derived 2-butyloctanol can be obtained.
• bio-derived branched primary alcohols having 6 to 12 carbon atoms that can be used to easily produce bio-derived ester compounds with reduced odor.
• the process for obtaining a bio-derived branched primary alcohol includes dimerizing a bio-derived linear primary alcohol, in particular the same bio-derived linear primary alcohol.
• the process for obtaining a bio-derived ester compound in the present invention is a process for obtaining a bio-derived ester compound using the bio-derived branched primary alcohol having 6 to 12 carbon atoms obtained in the above-mentioned process and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof.
• specific examples of the bio-derived branched primary alcohol having 6 to 12 carbon atoms obtained in the above-mentioned process include bio-derived 2-methylpentanol, bio-derived 2-ethylhexanol, bio-derived 2-propylheptanol, and bio-derived 2-butyloctanol, and one or more of these can be used.
• bio-derived branched primary alcohol having 6 to 12 carbon atoms it is preferable that 50% or more of the carbon atoms constituting the bio-derived branched primary alcohol having 6 to 12 carbon atoms are bio-derived carbon atoms, and it is preferable that all of the carbon atoms constituting the bio-derived branched primary alcohol having 6 to 12 carbon atoms are bio-derived carbon atoms.
• Examples of carboxylic acid compounds having a hydrocarbon group with 1 to 22 carbon atoms that can be used in the process of obtaining a bio-derived ester compound in the present invention include aliphatic monocarboxylic acids having a linear saturated aliphatic hydrocarbon group with 1 to 22 carbon atoms, aliphatic monocarboxylic acids having a branched saturated aliphatic hydrocarbon group with 4 to 22 carbon atoms, aliphatic monocarboxylic acids having a linear unsaturated aliphatic hydrocarbon group with 2 to 22 carbon atoms, aliphatic monocarboxylic acids having a branched unsaturated aliphatic hydrocarbon group with 4 to 22 carbon atoms, alicyclic monocarboxylic acids having an alicyclic hydrocarbon group with 4 to 22 carbon atoms, and aromatic monocarboxylic acids having an aromatic hydrocarbon group with 6 to 22 carbon atoms, and one or more of these can be used.
• examples of anhydrides of carboxylic acids having a hydrocarbon group with 1 to 22 carbon atoms that can be used in the present invention include the anhydrides of the above-mentioned carboxylic acids, and one or more of these can be used.
• carboxylic acid compounds having a hydroxy group, an aldehyde group, a carbonyl group, an ester bond, an ether bond, or the like in the molecule of each of the above-mentioned carboxylic acids, and it is also possible to use carboxylic acid compounds having two or more carboxy groups in the molecule.
• the methyl esters and ethyl esters of the above-mentioned carboxylic acids having a hydrocarbon group with 1 to 22 carbon atoms can also be used as carboxylic acid compounds having a hydrocarbon group with 1 to 22 carbon atoms.
• Aliphatic monocarboxylic acids having a linear saturated aliphatic hydrocarbon group with 1 to 22 carbon atoms can be used without any particular limitation as long as they have a linear saturated aliphatic hydrocarbon group with 1 to 22 carbon atoms and one carboxy group in the molecule and belong to the acyclic aliphatic compounds defined in the IUPAC Compendium of Chemical Terminology, second edition (1997).
• Such compounds include aliphatic monocarboxylic acid compounds consisting of a linear saturated aliphatic hydrocarbon group with 1 to 22 carbon atoms and one carboxy group, and aliphatic hydroxymonocarboxylic acid compounds consisting of a linear saturated aliphatic hydrocarbon group with 1 to 22 carbon atoms, one carboxy group, and one hydroxy group.
• examples of the aliphatic monocarboxylic acid compound consisting of a straight-chain saturated aliphatic hydrocarbon group having 1 to 22 carbon atoms and one carboxy group include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid (arachidic acid), eicosanoic acid, heneicosanoic acid (behenic acid), and heneicosanoic acid.
• examples of the aliphatic hydroxymonocarboxylic acid compound comprising a linear saturated aliphatic hydrocarbon group having 1 to 22 carbon atoms, one carboxy group, and one hydroxy group include hydroxyacetic acid, 2-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, 5-hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 7-hydroxyoctanoic acid, 8-hydroxynonanoic acid, 9-hydroxydecanoic acid, 10-hydroxyundecanoic acid, 11-hydroxydodecanoic acid, 12-hydroxytridecanoic acid, 13-hydroxytetradecanoic acid, 14-hydroxypentadecanoic acid, 15-hydroxyhexadecanoic acid, 16-hydroxyheptadecanoic acid, 17-hydroxyoctadecanoic acid, 18-hydroxynonadecanoic acid, 19-hydroxyicosanoic acid, 20-hydroxyeicosanoic acid, 21-
• an aliphatic monocarboxylic acid compound consisting of a linear saturated aliphatic hydrocarbon group having 8 to 20 carbon atoms and one carboxy group
• an aliphatic hydroxymonocarboxylic acid compound consisting of a linear saturated aliphatic hydrocarbon group having 8 to 20 carbon atoms, one carboxy group, and one hydroxy group
• an aliphatic hydroxymonocarboxylic acid compound consisting of a linear saturated aliphatic hydrocarbon group having 10 to 18 carbon atoms, one carboxy group, and one hydroxy group
• Aliphatic monocarboxylic acids having a branched saturated aliphatic hydrocarbon group with 4 to 22 carbon atoms can be used without any particular limitation as long as they have a branched saturated aliphatic hydrocarbon group with 4 to 22 carbon atoms and one carboxy group in the molecule and belong to the acyclic aliphatic compounds defined in the IUPAC Compendium of Chemical Terminology, second edition (1997).
• Such compounds include aliphatic monocarboxylic acid compounds consisting of a branched saturated aliphatic hydrocarbon group with 4 to 22 carbon atoms and one carboxy group, and aliphatic monocarboxylic acid compounds consisting of a branched saturated aliphatic hydrocarbon group with 4 to 22 carbon atoms, one carboxy group, and one hydroxy group.
• examples of the aliphatic monocarboxylic acid compound consisting of a branched saturated aliphatic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group include isopentanoic acid, isohexanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, isoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, isoundecanoic acid, isododecanoic acid, isotridecanoic acid, isotetradecanoic acid, isopentadecanoic acid, isohexadecanoic acid, isoheptadecanoic acid, isooctadecanoic acid, isonadecanoic acid, isoicosanoic acid, isoeicosanoic acid, isoheneicosanoic acid, and isohen
• examples of the aliphatic monocarboxylic acid compound comprising a branched saturated aliphatic hydrocarbon group having 4 to 22 carbon atoms, one carboxy group, and one hydroxy group include the above-mentioned aliphatic monocarboxylic acid compound comprising a branched saturated aliphatic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group, in which one hydrogen atom is substituted with a hydroxy group.
• an aliphatic monocarboxylic acid compound consisting of a branched saturated aliphatic hydrocarbon group having 8 to 20 carbon atoms and one carboxy group
• an aliphatic monocarboxylic acid compound consisting of a branched saturated aliphatic hydrocarbon group having 8 to 20 carbon atoms, one carboxy group, and one hydroxy group
• an aliphatic monocarboxylic acid compound consisting of a branched saturated aliphatic hydrocarbon group having 10 to 18 carbon atoms, one carboxy group, and one hydroxy group
• Aliphatic monocarboxylic acids having a linear unsaturated aliphatic hydrocarbon group with 2 to 22 carbon atoms can be used without any particular limitation as long as they have a linear unsaturated aliphatic hydrocarbon group with 2 to 22 carbon atoms and one carboxy group in the molecule and belong to the acyclic aliphatic compounds defined in the IUPAC Compendium of Chemical Terminology, second edition (1997).
• Such compounds include aliphatic monocarboxylic acid compounds consisting of a linear unsaturated aliphatic hydrocarbon group with 2 to 22 carbon atoms and one carboxy group, and aliphatic monocarboxylic acid compounds consisting of a linear unsaturated aliphatic hydrocarbon group with 2 to 22 carbon atoms, one carboxy group, and one hydroxy group.
• examples of the aliphatic monocarboxylic acid compound consisting of a straight-chain unsaturated aliphatic hydrocarbon group having 2 to 22 carbon atoms and one carboxy group include propenoic acid, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, icosenoic acid, eicosenoic acid, heneicosenoic acid, heneicosenoic acid, and isomers thereof, and more specifically, examples of the aliphatic monocarboxylic acid compound include 2-propenoic acid, 3-butenoic acid
• oleic acid examples include oleic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, palmitoleic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, oleic acid, elaidic acid, paxenoic acid, linoleic acid, ⁇ -linolenic acid, ⁇ -linolenic acid, 17-octadecenoic acid, 18-nonadecenoic acid, arachidonic acid, eicosapentaenoic acid, 19-icosenoic acid, 20-eicosenoic acid, 21-heneicosenoic acid, erucic acid, docosahe
• examples of the aliphatic monocarboxylic acid compound comprising a linear unsaturated aliphatic hydrocarbon group having 2 to 22 carbon atoms, one carboxy group, and one hydroxy group include the above-mentioned aliphatic monocarboxylic acid compound comprising a linear unsaturated aliphatic hydrocarbon group having 2 to 22 carbon atoms and one carboxy group, in which one hydrogen atom is substituted with a hydroxy group.
• the present invention from the viewpoint of easily obtaining a bio-derived ester compound with reduced odor, it is preferable to use one or more selected from the group consisting of an aliphatic monocarboxylic acid compound consisting of a linear unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms and one carboxy group, and an aliphatic hydroxymonocarboxylic acid compound consisting of a linear unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms, one carboxy group, and one hydroxy group, it is more preferable to use one or more selected from the group consisting of an aliphatic monocarboxylic acid compound consisting of a linear unsaturated aliphatic hydrocarbon group having 10 to 18 carbon atoms and one carboxy group, and an aliphatic hydroxymonocarboxylic acid compound consisting of a linear unsaturated aliphatic hydrocarbon group having 10 to 18 carbon atoms, one carboxy group, and one hydroxy group, it is even more prefer
• Aliphatic monocarboxylic acids having a branched unsaturated aliphatic hydrocarbon group with 4 to 22 carbon atoms can be used without any particular limitation as long as they have a branched unsaturated aliphatic hydrocarbon group with 4 to 22 carbon atoms and one carboxy group in the molecule and belong to the acyclic aliphatic compounds defined in the IUPAC Compendium of Chemical Terminology, second edition (1997).
• Such compounds include aliphatic monocarboxylic acid compounds consisting of a branched unsaturated aliphatic hydrocarbon group with 4 to 22 carbon atoms and one carboxy group, and aliphatic monocarboxylic acid compounds consisting of a branched unsaturated aliphatic hydrocarbon group with 4 to 22 carbon atoms, one carboxy group, and one hydroxy group.
• examples of the aliphatic monocarboxylic acid compound consisting of a branched unsaturated aliphatic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group include isopentenoic acid, isohexenoic acid, isoheptenoic acid, isooctenoic acid, isononenoic acid, isodecenoic acid, isoundecenoic acid, isododecenoic acid, isotridecenoic acid, isotetradecenoic acid, isopentadecenoic acid, isohexadecenoic acid, isoheptadecenoic acid, isooctadecenoic acid, isonadecenoic acid, isoicosenoic acid, isoeicosenoic acid, isoheneicosenoic acid, isoheneicosenoic acid, and isomers thereof.
• Examples of the aliphatic monocarboxylic acid compound consisting of a branched unsaturated aliphatic hydrocarbon group having 4 to 22 carbon atoms, one carboxy group, and one hydroxy group include the above-mentioned aliphatic monocarboxylic acid compound consisting of a branched unsaturated aliphatic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group, in which one hydrogen atom is substituted with a hydroxy group.
• the present invention from the viewpoint of easily obtaining a bio-derived ester compound with reduced odor, it is preferable to use one or more selected from the group consisting of an aliphatic monocarboxylic acid compound consisting of a branched unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms and one carboxy group, and an aliphatic monocarboxylic acid compound consisting of a branched unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms, one carboxy group, and one hydroxy group, it is more preferable to use one or more selected from the group consisting of an aliphatic monocarboxylic acid compound consisting of a branched unsaturated aliphatic hydrocarbon group having 10 to 18 carbon atoms and one carboxy group, and an aliphatic monocarboxylic acid compound consisting of a branched unsaturated aliphatic hydrocarbon group having 10 to 18 carbon atoms, one carboxy group, and one hydroxy group, it is even
• alicyclic monocarboxylic acid having an alicyclic hydrocarbon group having 4 to 22 carbon atoms there are no particular limitations on the compounds that can be used as long as they have an alicyclic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group in the molecule and belong to the alicyclic compounds defined in the IUPAC Compendium of Chemical Terminology, second edition (1997).
• examples of such compounds include alicyclic monocarboxylic acid compounds consisting of an alicyclic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group, and alicyclic monocarboxylic acid compounds consisting of an alicyclic hydrocarbon group having 4 to 22 carbon atoms, one carboxy group, and one hydroxy group.
• examples of the alicyclic monocarboxylic acid compound consisting of an alicyclic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group include methylcyclopropane carboxylic acid, ethylcyclopropane carboxylic acid, dimethylcyclopropane carboxylic acid, propylcyclopropane carboxylic acid, diethylcyclopropane carboxylic acid, butylcyclopropane carboxylic acid, t-butylcyclopropane carboxylic acid, pentylcyclopropane carboxylic acid, hexylcyclopropane carboxylic acid, heptylcyclopropane carboxylic acid, octylcyclopropane carboxylic acid, nonylcyclopropane carboxylic acid, decylcyclopropane carboxylic acid, undecylcyclopropane carboxylic acid, dodecylcyclopropane carboxylic acid, tri
• Examples of the alicyclic monocarboxylic acid compound comprising an alicyclic hydrocarbon group having 4 to 22 carbon atoms, one carboxy group, and one hydroxy group include the above-mentioned alicyclic monocarboxylic acid compound comprising an alicyclic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group, in which one hydrogen atom is substituted with a hydroxy group.
• an alicyclic monocarboxylic acid compound consisting of an alicyclic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group
• an alicyclic monocarboxylic acid compound consisting of an alicyclic hydrocarbon group having 4 to 22 carbon atoms, one carboxy group, and one hydroxy group
• an alicyclic monocarboxylic acid compound consisting of an alicyclic hydrocarbon group having 6 to 18 carbon atoms, one carboxy group, and one hydroxy group
• an alicyclic monocarboxylic acid compound consisting of an ali
• Aromatic monocarboxylic acids having an aromatic hydrocarbon group with 6 to 22 carbon atoms can be used without any particular limitation as long as they have an aromatic hydrocarbon group with 6 to 22 carbon atoms and one carboxy group in the molecule and belong to the aromatic compounds defined in the IUPAC Compendium of Chemical Terminology, second edition (1997).
• Examples of such compounds include aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group with 6 to 22 carbon atoms and one carboxy group, and aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group with 6 to 22 carbon atoms, one carboxy group, and one hydroxy group.
• aromatic monocarboxylic acid compounds include benzoic acid, o-hydroxybenzoic acid (salicylic acid), p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 3-hydroxy-o-toluic acid, 3-hydroxy-m-toluic acid, 3-hydroxy-p-toluic acid, o-ethylbenzoic acid, m-ethylbenzoic acid, p-ethylbenzoic acid, p-hydroxyethylbenzoic acid, o-propylbenzoic acid, m-propylbenzoic acid, p-propylbenzoic acid, p-hydroxypropylbenzoic acid, o-butylbenzoic acid, m-butylbenzoic acid, p-butylbenzoic acid, p-hydroxybutylbenzoic acid, p-hexylbenzoic acid,
• benzoic acid examples include benzoic acid, p-heptyl benzoic acid, p-hydroxyheptyl benzoic acid, p-octyl benzoic acid, p-hydroxyoctyl benzoic acid, p-ethylhexyl benzoic acid, p-nonyl benzoic acid, p-hydroxynonyl benzoic acid, p-decyl benzoic acid, p-hydroxydecyl benzoic acid, p-undecyl benzoic acid, p-hydroxyundecyl benzoic acid, p-dodecyl benzoic acid, p-hydroxydodecyl benzoic acid, p-tridecyl benzoic acid, p-hydroxytridecyl benzoic acid, p-tetradecyl benzoic acid, p-hydroxytetradecyl benzoic acid, p-pentadecyl benzo
• the present invention from the viewpoint of facilitating the production of a bio-derived ester compound with reduced odor, it is preferable to use one or more selected from the group consisting of aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group having 6 to 22 carbon atoms and one carboxy group, and aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group having 6 to 22 carbon atoms, one carboxy group, and one hydroxy group, and it is preferable to use one or more selected from the group consisting of aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group having 6 to 18 carbon atoms and one carboxy group, and aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group having 6 to 18 carbon atoms, one carboxy group, and one hydroxy group.
• aromatic monocarboxylic acid compounds having an aromatic hydrocarbon group with 6 to 10 carbon atoms and one carboxy group and aromatic monocarboxylic acid compounds having an aromatic hydrocarbon group with 6 to 10 carbon atoms, one carboxy group, and one hydroxy group
• aromatic monocarboxylic acid compounds having an aromatic hydrocarbon group with 6 to 10 carbon atoms, one carboxy group, and one hydroxy group and it is particularly preferable to use an aromatic monocarboxylic acid compound having an aromatic hydrocarbon group with 6 to 10 carbon atoms, one carboxy group, and one hydroxy group.
• carboxylic acid compounds having a hydrocarbon group of 1 to 22 carbon atoms or their anhydrides are used: an aliphatic monocarboxylic acid compound and its anhydride consisting of a linear saturated aliphatic hydrocarbon group having 1 to 22 carbon atoms and one carboxy group, an aliphatic monocarboxylic acid compound and its anhydride consisting of a branched saturated aliphatic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group, an aliphatic monocarboxylic acid compound and its anhydride consisting of a linear unsaturated aliphatic hydrocarbon group having 2 ...
• unsaturated aliphatic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group It is preferable to use one or more selected from the group consisting of aliphatic monocarboxylic acid compounds and anhydrides thereof consisting of a linear saturated aliphatic hydrocarbon group having 1 to 22 carbon atoms and one carboxy group, alicyclic monocarboxylic acid compounds and anhydrides thereof consisting of an alicyclic hydrocarbon group having 4 to 22 carbon atoms and one carboxy group, and aromatic monocarboxylic acid compounds and anhydrides thereof consisting of an aromatic hydrocarbon group having 6 to 22 carbon atoms, one carboxy group and one hydroxy group, and it is also preferable to use one or more selected from the group consisting of aliphatic monocarboxylic acid compounds and anhydrides thereof consisting of a linear saturated aliphatic hydrocarbon group having 1 to 22 carbon atoms and one carboxy group, and aromatic monocarboxylic acid compounds and anhydrides thereof consisting of an aromatic hydrocarbon group having 6 to 22 carbon
• aliphatic monocarboxylic acid compounds and anhydrides thereof consisting of a linear saturated aliphatic hydrocarbon group having 8 to 20 carbon atoms and one carboxy group
• aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group having 6 to 16 carbon atoms, one carboxy group, and one hydroxy group
• aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group having 6 to 12 carbon atoms and one hydroxy group is more preferable to use one or more selected from the group consisting of aliphatic monocarboxylic acid compounds and anhydrides thereof consisting of a linear saturated aliphatic hydrocarbon group having 8 to 20 carbon atoms and one carboxy group, and aromatic monocarboxylic acid compounds consisting of an aromatic hydrocarbon group having 6 to 16
• an aliphatic monocarboxylic acid compound consisting of a linear saturated aliphatic hydrocarbon group having 11 to 17 carbon atoms and one carboxy group
• an aromatic monocarboxylic acid compound consisting of an aromatic hydrocarbon group having 6 to 10 carbon atoms, one carboxy group, and one hydroxy group
• the carboxylic acid compound having a hydrocarbon group of 1 to 22 carbon atoms or its anhydride used in the present invention may be derived from a petroleum source or may be derived from a bio-source obtained from a plant resource or the like, but from the viewpoint of environmental consideration, it is preferable that 50% or more of the carbon atoms constituting the carboxylic acid compound having a hydrocarbon group of 1 to 22 carbon atoms or its anhydride are derived from a bio-source, and it is more preferable that all of the carbon atoms are derived from a bio-source.
• an ester compound As a method for producing an ester compound, a method is also envisaged in which a petroleum-derived, bio-based branched primary alcohol having 6 to 12 carbon atoms produced by the oxo process from petroleum-derived propylene and the like, and a bio-based carboxylic acid compound or anhydride having a hydrocarbon group having 1 to 22 carbon atoms are used to obtain an ester compound with reduced odor.
• this method cannot produce a bio-based ester compound with reduced odor.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is not particularly limited, and any known method can be used.
• a method of reacting a bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof by a known esterification reaction can be used.
• Such methods include a method of mixing a bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the presence of a solvent, catalyst, etc., as necessary, and reacting them at room temperature or by heating in a reduced pressure environment, normal pressure environment, or pressurized environment.
• Solvents that can be used in the esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof are not particularly limited as long as they are known solvents that can be used in esterification reactions, and examples of such solvents include hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ethylbenzene, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, acetone, and methyl ethyl ketone, and one or more of these can be used.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the absence of a solvent.
• the amount of the solvent is not particularly limited and can be adjusted appropriately depending on the purpose.
• the amount of the solvent used is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, and even more preferably 3 to 200 parts by mass, when the total amount of the bio-derived branched primary alcohol having 6 to 12 carbon atoms and the carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or anhydride thereof used is taken as 100 parts by mass.
• Catalysts that can be used in the esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof are not particularly limited as long as they are known catalysts that can be used in esterification reactions, and examples of such catalysts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, paratoluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, methylphosphonic acid, phenylphosphonic acid, aluminum lactate, lithium fluoride,
• the cation exchange resin include potassium chloride, cesium chloride, calcium chlor
• One or more of these may be used.
• it is preferable to use one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, methanesulfonic acid, paratoluenesulfonic acid, tetrapropyl titanate, zirconium octylate, and oxozirconium octylate as the catalyst and it is more preferable to use one or more selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, and zirconium octylate.
• the amount of the catalyst is not particularly limited and can be adjusted appropriately depending on the purpose.
• the amount of the catalyst used is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.1 to 5 parts by mass, and particularly preferably 0.2 to 3 parts by mass, when the total amount of the bio-derived branched primary alcohol having 6 to 12 carbon atoms and the carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or anhydride thereof used is taken as 100 parts by mass.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the presence of a catalyst.
• the temperature for reacting the bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or its anhydride is not particularly limited and can be adjusted appropriately depending on the purpose, etc., but can be, for example, room temperature to 300°C.
• the temperature for reacting the bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or its anhydride is preferably 50 to 260°C, more preferably 60 to 220°C, even more preferably 70 to 200°C, and particularly preferably 80 to 160°C.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof under a heated environment.
• the reaction time when reacting a bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is not particularly limited and can be adjusted appropriately depending on the purpose, for example, it can be 10 minutes to 72 hours.
• the reaction time when reacting a bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is preferably 1 hour to 48 hours, more preferably 2 hours to 24 hours.
• the esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is carried out in a reduced pressure environment
• the pressure is not particularly limited and can be adjusted appropriately depending on the purpose, but for example, the esterification reaction can be carried out in a pressure environment of 0.01 Pa to 80,000 Pa.
• the pressure is not particularly limited and can be adjusted appropriately depending on the purpose, but for example, the esterification reaction can be carried out in an environment pressurized to 0.001 MPa to 10 MPa with atmospheric pressure as the standard.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof under normal pressure.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the presence of a catalyst and in the absence of a solvent.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the presence of a catalyst under normal pressure.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the presence of a catalyst under a heated environment.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the presence of a catalyst, in a heated environment, and in the absence of a solvent.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the presence of a catalyst under a heated environment and under normal pressure.
• the method for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is a method for carrying out an esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in the presence of a catalyst, in a heated environment, in the absence of a solvent, and in a normal pressure environment.
• a method of reacting a bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound or anhydride thereof having a hydrocarbon group having 1 to 22 carbon atoms is preferably used, in which the mixture is heated to 60 to 300°C in the presence of a catalyst as necessary and reacted for 1 to 48 hours to react with the bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound or anhydride thereof having a hydrocarbon group having 1 to 22 carbon atoms, and more preferably used, a method of reacting a bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound or anhydride thereof having a hydrocarbon group having 1 to 22 carbon atoms by heating to 80 to 220°C in the presence of a catalyst and reacting for 2 to 24 hours.
• the ratio of the bio-derived branched primary alcohol having 6 to 12 carbon atoms and the carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof used is not particularly limited, but from the viewpoint of obtaining a bio-derived ester compound with reduced odor in high yield, for example, it is preferable to use a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof in a molar ratio of 20:1 to 1:10, more preferably a molar ratio of 10:1 to 1:5, even more preferably a molar ratio of 5:1 to 1:2, and particularly preferably a molar ratio of 3:1 to 1:1.
• bio-derived branched primary alcohol having 6 to 12 carbon atoms and the carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or the anhydride thereof may be mixed and reacted in one go, or the bio-derived branched primary alcohol having 6 to 12 carbon atoms and/or the carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or the anhydride thereof may be mixed and reacted in multiple batches.
• the esterification reaction between a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof is an equilibrium reaction, and therefore it is practically impossible to esterify the entire amount of the raw materials used.
• the reaction may be stopped at the stage when the esterification rate calculated based on the amount of the bio-derived branched primary alcohol having 6 to 12 carbon atoms and the carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or anhydride thereof used reaches a desired range, although this depends on the type and amount of the raw materials used and the reaction environment.
• the process for obtaining a bio-derived ester compound in the present invention may include a process for obtaining a bio-derived ester compound using a bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof, and may consist only of a process for obtaining a bio-derived ester compound by reacting a bio-derived branched primary alcohol having 6 to 12 carbon atoms with a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof, or may include a process for purifying the product by known methods such as filtration, centrifugation, oil-water separation, decantation, distillation, deodorization, and adsorption, as necessary.
• the distillation method that can be used in the process of obtaining the bio-derived ester compound of the present invention is not particularly limited and can be appropriately selected depending on the purpose.
• methods such as normal pressure distillation, reduced pressure distillation, molecular distillation, and steam distillation can be used. More specifically, methods such as single distillation, fractional distillation, flash distillation, steam distillation, vacuum distillation, short path distillation, thin film distillation, reactive distillation, and extractive distillation can be used.
• the deodorization method that can be used in the process of obtaining the bio-derived ester compound of the present invention is also not particularly limited and can be appropriately selected depending on the purpose.
• an adsorbent such as activated clay, activated carbon, magnesium silicate, aluminum silicate, aluminum phosphosilicate, magnesium hydroxide, aluminum hydroxide, magnesium oxide, aluminum oxide, zeolite, and silica gel is added, and the adsorbent is removed by a method such as filtration after stirring or leaving as necessary.
• a bio-derived branched primary alcohol having 6 to 12 carbon atoms is obtained by dimerizing one or more selected from the group consisting of a bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms, a bio-derived linear primary alcohol having a linear alkenyl group having 3 to 6 carbon atoms, a bio-derived linear aldehyde having a linear alkyl group having 3 to 6 carbon atoms, and a bio-derived linear aldehyde having a linear alkenyl group having 3 to 6 carbon atoms, and a bio-derived branched primary alcohol having 6 to 12 carbon atoms is obtained by dimerizing one or more selected from the group consisting of a bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms, a bio-derived linear aldehyde having a linear alkenyl group having 3 to 6 carbon atoms, and a bio-derived ester compound is obtained using the obtained
• the bio-derived ester compound of the present invention is a bio-derived ester compound produced by a method for producing a bio-derived ester compound, the method including: obtaining a bio-derived branched primary alcohol having 6 to 12 carbon atoms, the dimerization of one or more selected from the group consisting of the bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms, the bio-derived linear primary alcohol having a linear alkenyl group having 3 to 6 carbon atoms, the bio-derived linear aldehyde having a linear alkyl group having 3 to 6 carbon atoms, and the bio-derived linear aldehyde having a linear alkenyl group having 3 to 6 carbon atoms; and obtaining a bio-derived ester compound using the obtained bio-derived branched primary alcohol having 6 to 12 carbon atoms and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof.
• the bio-derived ester compound of the present invention contains a small amount of inevitable impurities derived from the raw materials. By identifying these inevitable impurities, it is possible to distinguish the ester compounds of the present invention from ester compounds obtained by production methods using petroleum raw materials, and from ester compounds obtained by production methods using bio-derived compounds different from the method of the present invention.
• the types and amounts of impurities contained vary depending on the type of plant resources used to obtain the bio-derived raw materials and the reaction pathway of the compounds, it is impossible and impractical to uniformly identify the types and amounts of inevitable impurities. For this reason, the bio-derived ester compounds of the present invention are identified by a production method that limits the raw materials.
• the form and embodiment of the use of the bio-derived ester compound of the present invention are not particularly limited, and can be used by blending it with cosmetics, detergents, paints, medicines, food, etc.
• the content of the bio-derived ester compound in a composition of a cosmetic, detergent, paint, medicine, food, etc. containing the bio-derived ester compound of the present invention is not particularly limited, and can be, for example, 0.001 to 70.0 mass% relative to the total amount of the composition, preferably 0.01 to 50.0 mass% relative to the total amount of the composition, more preferably 0.05 to 30.0 mass%, and even more preferably 0.10 to 20.0 mass%. Since the bio-derived ester compound of the present invention has reduced odor, even when it is contained in a composition, it can exhibit the desired properties while preventing adverse effects on the fragrance.
• composition containing the bio-derived ester compound of the present invention can be blended with various components to improve or modify various properties (solubility, dispersibility, stability, usability, applicability, penetration, moisture retention, safety, design, optical properties, fragrance, whitening, etc.) during storage, during use, and after use depending on the purpose of use.
• Such components include higher alcohols, powder components, higher fatty acids, moisturizing agents, water-soluble polymers, sequestering agents, water, oil components, lower alcohols, polyhydric alcohols, monosaccharides, oligosaccharides, polysaccharides, amino acids and their derivatives, organic amines, pH adjusters, vitamins, UV protection components, antioxidants, thickeners, surfactants, and other components that can be blended (preservatives, blood circulation promoters, anti-inflammatory agents, activators, whitening agents, antiseborrheic agents, anti-inflammatory agents, various extracts, and plant seaweed extracts, etc.), and one or more of these can be blended at will.
• higher alcohols include linear higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol; and branched higher alcohols such as monostearyl glycerin ether (batyl alcohol), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, and octyldodecanol. One or more of these can be used.
• linear higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol
• branched higher alcohols such as monostearyl glycerin ether (batyl alcohol), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol,
• the powder component may be, for example, inorganic powder (e.g., talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, red mica, black mica, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstate metal salts, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, zinc myristate, calcium palmitate, stearic acid, etc.) aluminum phosphate, boron nitride, etc.); organic powders (e.g., polyamide resin powder, polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene-acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene
• natural pigments e.g., chlorophyll, ⁇ -carotene, etc.
• higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), etc., and one or more of these can be used.
• lauric acid myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), etc.
• Humectants include, for example, polyethylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Rosa robur extract, Achillea millefolium extract, Melilot extract, etc., and one or more of these can be used.
• EO diglycerin
• Natural water-soluble polymers include, for example, plant-based polymers (e.g., gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed, algae colloid (cassow extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial-based polymers (e.g., xanthan gum, dextran, succinoglucan, pullulan, gellan gum, etc.); and animal-based polymers (e.g., collagen, casein, albumin, gelatin, etc.), and one or more of these can be used.
• plant-based polymers e.g., gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed, algae colloid (cassow extract), starch (rice, corn,
• water-soluble polymers examples include starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); alginic acid-based polymers (e.g., sodium alginate, propylene glycol alginate, etc.); vinyl-based polymers (e.g., polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, etc.); polyoxyethylene-based polymers (e.g., polyoxyethylene polyoxypropylene copolymers made from polyethylene glycol 20,000, 40,000, or 60,000); acrylic-based polymers (e.g., sodium polyacrylate, polye
• sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyltriacetate, etc., and one or more of these can be used.
• Oily ingredients include, for example, ester oils (excluding the bio-derived esters of the present invention), hydrocarbon oils, and silicone oils, and one or more of these can be used.
• ester oils include isopropyl myristate, cetyl octanoate, isononyl isononanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, glyceryl di-2-ethylhexanoate, dipentaerythritol fatty acid esters, glyceryl monoisostearate, neopentyl glycol dicaprate, di
• fatty acid esters examples include trimethylolpropane esters, pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, glyceryl trimyristate, glyceryl tri-2-heptylundecanoate, castor oil fatty acid methyl esters, oleyl oleate, acetoglyceride, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, ethyl laurate, diisopropyl sebacate, triethylhexanoin, and tri(caprylic acid/capric acid)glyce
• oils and fats that contain ester oils such as avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, triglyceride, cacao butter, coconut oil, hardened coconut oil, palm oil, palm kernel oil, Japanese wax kernel oil, hardened oil, Japanese wax, and hardened castor oil, can also be used.
• ester oils such as avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sa
• hydrocarbon oils examples include liquid paraffin, ozokerite, squalane, pristane, paraffin, isododecane, ceresin, squalene, petrolatum, microcrystalline wax, etc., and one or more of these can be used.
• silicone oils include linear polysiloxanes (e.g., dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxanes (e.g., octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), silicone resins that form a three-dimensional network structure, silicone rubber, various modified polysiloxanes (amino-modified polysiloxanes, polyether-modified polysiloxanes, alkyl-modified polysiloxanes, fluorine-modified polysiloxanes, etc.), and one or more of these can be used.
• linear polysiloxanes e.g., dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane
• lower alcohols examples include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, etc., and one or more of these can be used.
• polyhydric alcohols examples include dihydric alcohols (e.g., ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,2-hexanediol, etc.); trihydric alcohols (e.g., glycerin, trimethylolpropane, etc.); tetrahydric alcohols (e.g., pentaerythritol such as 1,2,6-hexanetriol, etc.); pentahydric alcohols (e.g., xylitol, etc.); hexahydric alcohols (e.g., sorbitol, mannitol, etc.); polyhydric alcohol polymers (e.g., diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); alkyl ethers
• monosaccharides examples include trioses (e.g., D-glyceryl aldehyde, dihydroxyacetone, etc.); tetraoses (e.g., D-erythrose, D-erythrulose, D-threose, erythritol, etc.); pentoses (e.g., L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.); hexoses (e.g., D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tag sugars (e.g., aldoheptose, heptose, etc.); octose (e.g., octo
• oligosaccharides include sucrose, umbelliferose, lactose, planteose, isolichinoses, ⁇ , ⁇ -trehalose, raffinose, lychinoses, umbilicin, stachyose, verbascoses, etc., and one or more of these can be used.
• polysaccharides examples include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, keratosulfate, locust bean gum, succinoglucan, and caronic acid, and one or more of these can be used.
• amino acids examples include neutral amino acids (e.g., threonine, cysteine, etc.); basic amino acids (e.g., hydroxylysine, etc.); and the like.
• amino acid derivatives include sodium acyl sarcosine (sodium lauroyl sarcosine), acyl glutamate, sodium acyl ⁇ -alanine, glutathione, pyrrolidone carboxylic acid, etc., and one or more of these can be used.
• organic amines examples include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, etc., and one or more of these can be used.
• pH adjusters examples include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate, and one or more of these can be used.
• vitamins examples include vitamins A, B1, B2, B6, C, E and their derivatives, pantothenic acid and its derivatives, biotin, etc., and one or more of these can be used.
• inorganic ultraviolet protection components such as powder pigments and metal powder pigments and surface-treated products thereof, as well as organic ultraviolet protection components can be used, for example, metal oxides such as titanium oxide, zinc oxide, cerium oxide, low-order titanium oxide, and iron-doped titanium oxide, metal hydroxides such as iron hydroxide, metal flakes such as plate-like iron oxide and aluminum flakes, ceramics such as silicon carbide, and products thereof that have been treated with fluorine compounds, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, silane treatment, oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment, or metal oxide treatment, as well as para-aminobenzoic acid, benzoic acid, etc.
• metal oxides such as titanium oxide, zinc oxide, cerium oxide, low-order titanium oxide, and iron-doped titanium oxide
• metal hydroxides such as iron hydroxide
• metal flakes such as plate-like iron oxide and aluminum flakes
• Examples include phenones, cinnamic acid, benzoylmethane, 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester, dimethoxybenzylidene dioxoimidazolidinepropionate 2-ethylhexyl, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, cinoxate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 3-(4-methylbenzylidene)camphor, octyl triazone, 4-(3,4-dimethoxyphenylmethylene)-2,5-dioxo-1-imidazolidinepropionate 2-ethylhexyl, and polymer derivatives thereof. One or more of these can be used.
• antioxidants examples include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, etc., and one or more of these can be used.
• Thickening agents include, for example, xanthan gum, carrageenan, high methoxyl pectin, low methoxyl pectin, guar gum, gum arabic, crystalline cellulose, arabinogalactan, karaya gum, tragacanth gum, alginic acid, albumin, casein, curdlan, ⁇ -glucan, ⁇ -glucan derivatives, gellan gum, dextran, ⁇ -glucose and ⁇ -glucose derivatives, cellulose or its derivatives, keratin and collagen or their derivatives, calcium alginate, pullulan, agar, gelatin, tamarind seed polysaccharide, carbomer, dimethyldiallylammonium chloride-acrylamide copolymer, dimethyldiallylammonium chloride hectorite, acrylamide-acrylic acid-dimethyldiallylammonium chloride copolymer, dibutylethylhexanoyl glutamide, and the
• Surfactants include, for example, cationic surfactants (e.g., lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyltrimethylammonium saccharin, cetyltrimethylammonium saccharin, behenyltrimethylammonium methylsulfate, behenyldimethylamine, behenic acid diethylaminoethylamide, behenic acid dimethylaminopropylamide, behenic acid dimethylaminoethylamide, stearyldimethylamine, palmitoxypropyldimethylamine, stearoxypropyldimethylamine, etc.); anionic surfactants (e.g., alkyl ether sulfates, alkyl sulfates, alkyl ether sulfate ester salts,
• ingredients include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.); anti-inflammatory agents (for example, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (for example, saxifrage extract, arbutin, etc.); various extracts (for example, Phellodendron bark, Coptis japonica, Lithospermum root, Peony root, Swertia japonica, Birch, sage, Loquat, Carrot, Aloe, Mallow, Iris, Grape, Coix seed, Loofah, Lily, Saffron, Cnidium rhizome, Angelica acutiloba, Hypericum perforatum, Ononis, Garlic, chili pepper, Citrus chinensis, Angelica acutiloba,
• the bio-derived ester compound of the present invention can also be used as an intermediate compound for obtaining a target compound by further reacting it with another raw material compound.
• the other raw material compound that can be used at this time is not particularly limited as long as it is a compound that reacts with the bio-derived ester compound of the present invention, and examples thereof include compounds having functional groups such as aldehyde groups and ketone groups in the molecule.
• the target compound obtained by such a method is also not particularly limited and can be appropriately selected according to the purpose. At this time, for example, when p-methoxybenzaldehyde is used as the other raw material compound, a methoxycinnamate ester can be obtained as the target compound.
• 2-ethylhexyl methoxycinnamate can be obtained by using 2-ethylhexyl acetate, which is a bio-derived ester compound, as an intermediate compound and p-methoxybenzaldehyde as the other raw material compound and reacting them by a known method.
• the target compound obtained by such a method uses a bio-derived ester compound with reduced odor as an intermediate compound, and therefore the obtained target compound can also be used as a compound with reduced odor.
• the form and embodiment of use of the target compound thus obtained is not particularly limited, and like the bio-derived ester compounds described above, it can be used by blending it into, for example, cosmetics, cleaning agents, paints, pharmaceuticals, foods, etc.
• a method for producing a bio-derived ester compound comprising: a step of obtaining a bio-derived branched primary alcohol having a branched alkyl group having 6 to 12 carbon atoms, the step comprising dimerizing one or more selected from the group consisting of a bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms, a bio-derived linear primary alcohol having a linear alkenyl group having 3 to 6 carbon atoms, a bio-derived linear aldehyde having a linear alkyl group having 3 to 6 carbon atoms, and a bio-derived linear aldehyde having a linear alkenyl group having 3 to 6 carbon atoms; and a step of obtaining a bio-derived ester compound using the obtained bio-derived branched primary alcohol and a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof.
• a method for producing a bio-derived ester compound according to (1) comprising a step of obtaining a bio-derived branched primary alcohol having a branched alkyl group having 6 to 12 carbon atoms, the step comprising dimerizing one or two selected from the group consisting of bio-derived linear primary alcohols having a linear alkyl group having 3 to 6 carbon atoms.
• a method for reducing the odor of an ester compound comprising reacting a bio-derived branched primary alcohol having a branched alkyl group having 6 to 12 carbon atoms as a raw material, wherein the bio-derived branched primary alcohol is obtained through a step of dimerizing one or more selected from the group consisting of a bio-derived linear primary alcohol having a linear alkyl group having 3 to 6 carbon atoms, a bio-derived linear primary alcohol having a linear alkenyl group having 3 to 6 carbon atoms, a bio-derived linear aldehyde having a linear alkyl group having 3 to 6 carbon atoms, and a bio-derived linear aldehyde having a linear alkenyl group having 3 to 6 carbon atoms, and the ester compound is obtained by reacting the bio-derived branched primary alcohol with a carboxylic acid compound having a hydrocarbon group having 1 to 22 carbon atoms or an anhydride thereof.
• Example 1 3,552 g of bio-derived n-butanol, 424 g of tripotassium phosphate, 448 g of calcium oxide, and 160 g of copper powder were added to an autoclave, and the mixture was reacted at 290° C. for 5 hours. The mixture was then filtered and distilled to obtain 1,248 g of bio-derived 2-ethylhexanol, which is a bio-derived branched primary alcohol formed by dimerization of bio-derived n-butanol, and 1,812 g of unreacted bio-derived n-butanol.
• Example 2 80 g of the bio-derived 2-ethylhexanol obtained in Example 1, 78 g of palmitic acid derived from petroleum raw materials, and 1.6 g of 98% sulfuric acid as a catalyst were added to another reaction vessel, and reacted at 90 ° C. for 5 hours to obtain 2-ethylhexyl palmitate in the reaction vessel. After cooling to room temperature, the resulting mixture was transferred to an oil-water separator, and 110 g of water and 2.6 g of 48% aqueous sodium hydroxide solution were added and stirred at 60 ° C. for 30 minutes. Then, the mixture was left to stand for 30 minutes to separate into a lower aqueous phase and an upper oil phase.
• the oil phase was then extracted and dehydrated by reducing pressure treatment at 60 ° C. and 27 kPa for 1 hour.
• 0.9 g of magnesium silicate and 0.9 g of aluminum silicate were added, and the mixture was stirred at 80 ° C. for 30 minutes.
• magnesium silicate and aluminum silicate were filtered off.
• the obtained filtrate was subjected to a reduced pressure treatment at 110 to 125°C and 4.0 kPa or less to remove unreacted bio-derived 2-ethylhexanol.
• 6.6 g of activated clay was added and stirred at 80°C for 30 minutes. After cooling to room temperature, the activated clay was filtered off to obtain 101 g of bio-derived 2-ethylhexyl palmitate B.
• Example 3 130 g of the bio-derived 2-ethylhexanol obtained in Example 1, 55 g of salicylic acid derived from petroleum raw materials, and 3.9 g of 98% sulfuric acid as a catalyst were added to a reaction vessel, and reacted at 90° C. for 24 hours to obtain 2-ethylhexyl salicylate in the reaction vessel. After cooling to room temperature, the resulting mixture was transferred to an oil-water separator, and 50 g of water and 2.4 g of 48% aqueous sodium hydroxide solution were added and stirred at 60° C. for 30 minutes. Then, the mixture was left to stand for 30 minutes to separate into a lower aqueous phase and an upper oil phase.
• the oil phase was then extracted and dehydrated by reducing pressure treatment at 60° C. and 27 kPa for 1 hour.
• 0.8 g of magnesium silicate and 0.8 g of aluminum silicate were added, and the mixture was stirred at 80° C. for 30 minutes.
• the magnesium silicate and aluminum silicate were filtered off.
• the obtained filtrate was subjected to a reduced pressure treatment at 110 to 125°C and 4.0 kPa or less to remove unreacted bio-derived 2-ethylhexanol.
• 3 g of activated clay was added and stirred at 80°C for 30 minutes. After cooling to room temperature, the activated clay was filtered off to obtain 85 g of bio-derived 2-ethylhexyl salicylate A.
• Example 4 130 g of the bio-derived 2-ethylhexanol obtained in Example 1, 55 g of petroleum-derived salicylic acid, and 0.28 g of zirconium octylate as a catalyst were added to a reaction vessel, and the mixture was reacted at 200°C for 8 hours to obtain 2-ethylhexyl salicylate in the reaction vessel. After cooling to room temperature, 3.4 g of aluminum silicate was added, and the mixture was stirred at 80°C for 30 minutes. After cooling to room temperature, the aluminum silicate was filtered off. The obtained filtrate was subjected to a reduced pressure treatment at 110 to 125°C and 4.0 kPa or less to remove unreacted bio-derived 2-ethylhexanol.
• Example 5 104 g of the bio-derived 2-ethylhexanol obtained in Example 1 and 103 g of bio-derived palmitic acid were added to a separate reaction vessel and reacted at 190° C. for 20 hours to obtain 2-ethylhexyl palmitate in the reaction vessel.
• the obtained filtrate was reduced in pressure to 4.0 kPa or less at 110 to 125° C. to remove unreacted bio-derived 2-ethylhexanol.
• 4.4 g of activated clay was added and stirred at 80° C. for 30 minutes. After cooling to room temperature, the activated clay was filtered off to obtain 137 g of bio-derived 2-ethylhexyl palmitate C.
• Petroleum-derived 2-ethylhexyl palmitate A' was obtained by the same method as in Example 1, except that 104 g of petroleum-derived 2-ethylhexanol was used, which was produced by producing n-butyraldehyde from petroleum-derived propylene using the Oxo process, followed by aldol condensation of the n-butyraldehyde and hydrogenation, instead of the bio-derived 2-ethylhexanol.
• Petroleum-derived 2-ethylhexyl palmitate B' was obtained by the same method as in Example 2, except that 80 g of petroleum-derived 2-ethylhexanol was used, which was produced by producing n-butyraldehyde from petroleum-derived propylene using the Oxo process, followed by aldol condensation of the n-butyraldehyde and hydrogenation, instead of the bio-derived 2-ethylhexanol.
• Petroleum-derived 2-ethylhexyl salicylate A' was obtained in the same manner as in Example 3, except that 130 g of petroleum-derived 2-ethylhexanol was used, which was produced by producing n-butylaldehyde from petroleum-derived propylene using the Oxo process, followed by aldol condensation of the n-butylaldehyde and hydrogenation, instead of the bio-derived 2-ethylhexanol.
• Petroleum-derived 2-ethylhexyl salicylate B' was obtained in the same manner as in Example 4, except that 130 g of petroleum-derived 2-ethylhexanol was used, which was produced by producing n-butylaldehyde from petroleum-derived propylene using the Oxo process, followed by aldol condensation of the n-butylaldehyde and hydrogenation, instead of the bio-derived 2-ethylhexanol.
• Petroleum-derived 2-ethylhexyl palmitate C' was obtained in the same manner as in Example 5, except that 104 g of petroleum-derived 2-ethylhexanol was used, which was produced by producing n-butyraldehyde from petroleum-derived propylene using the Oxo process, followed by aldol condensation of the n-butyraldehyde and hydrogenation, instead of the bio-derived 2-ethylhexanol.
• the odor of the ester compounds produced in Examples 1 to 5 and Comparative Examples 1 to 5 was evaluated immediately after production. Specifically, seven examiners checked the odor of each produced ester compound, scored the ester compound with the least odor scored as 4, and scored 10 samples on a four-point scale from 1 to 4. The total score of the scores of each examiner was calculated, and the odor was evaluated as follows: if the total score was 24 or more, it was rated as excellent; if the total score was 18 or more and less than 24, it was rated as good; if the total score was less than 18, it was rated as bad. The evaluation results are shown in Table 1. Note that if the total score is less than 18 in this evaluation, it indicates that the obtained ester compound has poor odor and is therefore poor in practical use.

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