WO2024090423A1 - Composition contenant un (méth)acrylate - Google Patents

Composition contenant un (méth)acrylate Download PDF

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WO2024090423A1
WO2024090423A1 PCT/JP2023/038309 JP2023038309W WO2024090423A1 WO 2024090423 A1 WO2024090423 A1 WO 2024090423A1 JP 2023038309 W JP2023038309 W JP 2023038309W WO 2024090423 A1 WO2024090423 A1 WO 2024090423A1
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meth
acrylate
general formula
carbon atoms
polymer
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PCT/JP2023/038309
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English (en)
Japanese (ja)
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英明 長野
大谷　巌
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株式会社日本触媒
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a composition containing a novel (meth)acrylate, a method for producing the composition, and a water/oil repellent using the (meth)acrylate.
  • a fluorine-based water and oil repellent composition that combines a higher alkyl (meth)acrylate and a fluorine-based polyfluoroalkyl (meth)acrylate is introduced in the following Patent Document 1.
  • JP 2002-201463 A Japanese Patent Application Laid-Open No. 08-071429 JP 2002-326974 A Japanese Patent Application Laid-Open No. 6-33043 Japanese Patent Application Laid-Open No. 11-349987 Japanese Patent Application Laid-Open No. 10-167990 Japanese Patent No. 2703752 JP 2023-78348 A
  • long-chain alkyl (meth)acrylates are used as components of water and oil repellent compositions.
  • Long-chain alkyl acrylates have melting points that solidify in winter, with acrylates with 12 alkyl carbon atoms at about 4°C, acrylates with 14 carbon atoms at about 14°C, acrylates with 16 carbon atoms at about 17°C, and acrylates with 18 carbon atoms at about 28°C. Therefore, when removing products filled in drums in winter, they must be heated to a temperature above their melting point. However, if heated to a temperature higher than the melting point, this product contains polymerizable groups, and polymerization will begin when heated, causing heat to build up inside the drum, which may lead to an explosion. For this reason, they are difficult to handle, as they must be dissolved slowly over a period of time at a temperature 20°C to 30°C higher than the melting point.
  • a novel (meth)acrylate compound represented by general formula (1) has a similar structure to long-chain alkyl (meth)acrylates, but has physical properties with a lower melting point and can be handled without heating, making it easy to handle. They have also found that the novel (meth)acrylate compound is effective as a water and oil repellent. Based on this knowledge, the inventors have completed the present invention.
  • composition containing a novel compound that is easy to handle, as well as its manufacturing method and uses.
  • FIG. 1 is a chart obtained by carrying out H-NMR measurement on the reaction product ((2-[(1-methylundecyl)oxy]ethyl acrylate) isomer mixture) obtained in Example 1.
  • FIG. 2 is a chart obtained by carrying out H-NMR measurement on the reaction product ((2-[(1-methyltridecyl)oxy]ethyl acrylate) isomer mixture) obtained in Example 3.
  • FIG. 3 is a chart obtained by carrying out H-NMR measurement on the acrylate polymer obtained in Example 4.
  • (Definition) "(Meth)acrylic” means “acrylic or methacrylic”. "(Meth)acrylate” means “acrylate or methacrylate”.
  • structural unit derived from a monomer means a structural unit formed by polymerization of a monomer, and more specifically, means a structure formed by cleavage of a carbon-carbon double bond of a monomer.
  • a (meth)acrylate-containing composition comprising two or more isomers of a (meth)acrylate represented by the following general formula (1), the isomer (A) being an isomer in which R2 is a methyl group, and the isomer (B) being an isomer in which R2 is an alkyl group having two or more carbon atoms:
  • R1 represents a hydrogen atom or a methyl group.
  • R2 and R3 represent alkyl groups, and the total number of carbon atoms of R2 and R3 is 6 to 22.
  • n is a number from 1 to 3.
  • R2 and R3 are alkyl groups, the total number of carbon atoms of R2 and R3 is 6 to 22, and n is a number from 1 to 3.
  • R2 and R3 are alkyl groups, the total number of carbon atoms of R2 and R3 is 6 to 22, and n is a number from 1 to 3.
  • R1 represents a hydrogen atom or a methyl group
  • R4 represents an alkyl group having 1 to 8 carbon atoms.
  • a method for imparting water and oil repellency to a substrate comprising a step of adhering the polymer according to [8] or [9] above to the substrate.
  • composition of the present invention relates to a composition (hereinafter also referred to as the "(meth)acrylate composition of the present invention") containing two or more isomers that are (meth)acrylate compounds (hereinafter also referred to as the "(meth)acrylate of the present invention”), and a production method thereof, and the compounds (isomers) are commonly represented by the following general formula (1).
  • R1 is a hydrogen atom or a methyl group
  • R2 and R3 are alkyl groups
  • the total number of carbon atoms of R2 and R3 is 6 to 22
  • n is a number from 1 to 3.
  • the (meth)acrylate composition of the present invention contains the above-mentioned isomer (A) in which R2 is a methyl group and the above-mentioned isomer (B) in which R2 is an alkyl group having 2 or more carbon atoms.
  • R3 in the isomers (A) and (B) is not particularly limited as long as the total carbon number of R2 and R3 is the same in the isomers (A) and (B) and is in the range of 6 to 22.
  • the (meth)acrylate composition of the present invention contains two or more types of such isomers, and thus has lower crystallinity and a lower melting point than when only one type of isomer is contained, thereby sufficiently suppressing freezing in winter and providing excellent handleability.
  • the (meth)acrylate represented by the above general formula (1) has a branched alkyl group at the ethylene glycol terminal, and therefore tends to have a higher glass transition temperature than those having a linear alkyl group.
  • the (meth)acrylate composition of the present invention preferably contains 1 to 50 mol % of the isomer (A) in which R 2 is a methyl group, and 50 to 99 mol % of the isomer (B) in which R 2 is an alkyl group having 2 or more carbon atoms. More preferably, the (meth)acrylate composition contains 2 to 40 mol % of the isomer (A) in which R 2 is a methyl group, and 60 to 98 mol % of the isomer (B) in which R 2 is an alkyl group having 2 or more carbon atoms.
  • the (meth)acrylate composition contains 5 to 30 mol % of the isomer (A) in which R 2 is a methyl group, and 70 to 95 mol % of the isomer (B) in which R 2 is an alkyl group having 2 or more carbon atoms.
  • the above-mentioned isomer (B) may be one or more kinds of compounds, so long as it is a compound corresponding to an isomer of the above-mentioned isomer (A).
  • the composition preferably consists essentially of the (meth)acrylate compound of the present invention, and contains the (meth)acrylate compound in an amount of 90 mol % or more, desirably 95 mol % or more, and more preferably 98 mol % or more.
  • the proportion of the (meth)acrylate compound of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on 100% by mass of the composition.
  • the total number of carbon atoms in R2 and R3 in the above general formula (1) is preferably 7 to 21, more preferably 9 to 19, and even more preferably 11 to 17. If the total number of carbon atoms in R2 and R3 is less than 6, the water and oil repellency will be reduced, which is not preferable. Also, if the total number of carbon atoms in R2 and R3 exceeds 22, the availability of olefins with that number of carbon atoms will be reduced.
  • R2 and R3 are alkyl groups, and are not particularly limited as long as the total number of carbon atoms of R2 and R3 is 6 to 22.
  • the alkyl group may be any of linear, branched, and cyclic, but it is preferable that R2 and R3 are each a linear alkyl group. That is, the (meth)acrylate of the present invention preferably has a secondary alkyl group at the ethylene glycol terminal.
  • R2 in the above isomer (B) is an alkyl group having 2 or more carbon atoms, and the total number of carbon atoms of R2 and R3 may be the same as that of isomer (A), but is preferably an alkyl group having 8 to 20 carbon atoms. More preferred examples of R2 in the above isomer (B) are ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.
  • n is the repeating unit (number of moles added) of the ethylene glycol chain, and is a number from 1 to 3. However, a larger n is not preferred because it increases the affinity for water. For this reason, n is preferably 1 to 2, and more preferably 1 to 1.5.
  • compositions of the present invention may include any compound.
  • the composition of the present invention may contain a compound represented by the following general formula (2).
  • the composition of the present invention is not particularly limited, but the content of the compound represented by the following general formula (2) is preferably 0 to 10 mass % relative to 100 mass % of the compound represented by the above general formula (1).
  • the composition of the present invention may contain a polymerization inhibitor.
  • the composition of the present invention is not particularly limited, but it is preferable that the polymerization inhibitor is contained in a ratio of 0.00001% or more and 5% or less by mass based on 100% by mass of the compound represented by the above general formula (1). If it is within the above range, the storage stability of the composition of the present invention tends to be improved.
  • the polymerization inhibitor is not particularly limited, but examples thereof include the compounds described below.
  • composition of the present invention may contain a polymerization initiator.
  • polymerization initiators include compounds that generate radicals when exposed to heat or light. Specific examples include the polymerization initiators described below.
  • the content ratio of the polymerization initiator is not particularly limited, but the composition of the present invention preferably contains the polymerization initiator in a ratio of 0.01% by mass or more and 5% by mass or less relative to 100% by mass of the compound represented by the above general formula (1). If it is within the above range, there is a tendency that the polymerization of the composition of the present invention will be less delayed.
  • the composition of the present invention may contain a radical polymerizable compound other than the compound represented by the above general formula (1).
  • the radical polymerizable compound include compounds that undergo radical polymerization by heat or light. Specific examples include the monomers described below.
  • the composition of the present invention is not particularly limited, but the ratio of the radical polymerizable compound other than the compound represented by the above general formula (1) to 100% by mass of the compound represented by the above general formula (1) is preferably 0% by mass or more and 99% by mass or less, more preferably 0 to 80% by mass, even more preferably 0 to 60% by mass, still more preferably 0 to 40% by mass, still more preferably 0 to 20% by mass, and particularly preferably 0 to 10% by mass.
  • the composition of the present invention may contain a polymer having a weight average molecular weight of 2000 or less, such as a polymer of (meth)acrylic acid or a polymer of alkyl (meth)acrylate, but the content of the polymer is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the compound represented by the above general formula (1).
  • the weight average molecular weight can be measured by gel permeation chromatography or a static light scattering method.
  • the (meth)acrylate-containing composition of the present invention can be produced by esterification or transesterification as described below.
  • the mixing ratio of the (meth)acrylate isomers in the (meth)acrylate composition of the present invention is derived from the mixing ratio of the isomers of the alcohols described below used as raw materials (and further the mixing ratio of the isomers of the olefins used as raw materials for the alcohols).
  • the present invention also relates to a method for producing a (meth)acrylate-containing composition, comprising: a step of heat-treating a mixture containing an alcohol represented by general formula (2) and a polymerization inhibitor; and a step of adding (meth)acrylic acid and an esterification catalyst to the composition containing the alcohol represented by general formula (2) obtained by the heat-treatment step, thereby carrying out an esterification reaction.
  • the present invention also relates to a method for producing a (meth)acrylate-containing composition, the method comprising: a step of heat-treating a mixture containing an alcohol represented by the above general formula (2) and a polymerization inhibitor; and a step of adding a (meth)acrylic acid ester represented by the following general formula (3) and an ester exchange catalyst to the composition containing the alcohol represented by the general formula (2) obtained by the heat treatment step, thereby carrying out an ester exchange reaction.
  • R2 and R3 are alkyl groups, the total number of carbon atoms of R2 and R3 is 6 to 22, and n is a number from 1 to 3.
  • R1 represents a hydrogen atom or a methyl group
  • R4 represents an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms may be straight-chain, branched or cyclic.
  • the alcohol used as a raw material for the (meth)acrylate represented by the general formula (1) in the present invention is the alcohol represented by the above general formula (2).
  • the total number of carbon atoms in R 2 and R 3 is preferably 7 to 21, more preferably 9 to 19, and even more preferably 11 to 17.
  • n is preferably 1 to 2, and more preferably 1 to 1.5.
  • alcohols encompassing the general formula (2) can be synthesized by various methods, such as a method of adding an alkylene oxide to a higher alcohol, a method of dehydrating and condensing a higher alcohol with a (poly)alkylene glycol, a method of condensing a chlorinated paraffin with a (poly)alkylene glycol, and a method of adding a (poly)alkylene glycol to a long-chain olefin.
  • the method of adding an alkylene oxide to a higher alcohol or the method of dehydrating and condensing a higher alcohol with a (poly)alkylene glycol generally results in a long polyethylene glycol chain length (n in general formula (2)) unlike the structure of general formula (2), which is undesirable because it increases the affinity for water.
  • the method of obtaining the structure of the general formula (2) by condensing chlorinated paraffin with (poly)alkylene glycol it is possible to synthesize the structure, but there is a concern that waste containing chlorine will be generated. For this reason, the method of adding (poly)alkylene glycol to long-chain olefin is preferable.
  • the method described in JP-A-11-349987, JP-A-10-167990, and Japanese Patent No. 2703752 can be adopted.
  • an olefin having 7 to 23 carbon atoms and ethylene glycol can be used as raw materials for synthesizing the alcohol represented by the general formula (2).
  • a 1-olefin having 7 to 23 carbon atoms and ethylene glycol can be used as the raw material for synthesizing the alcohol in which R2 is a methyl group.
  • the 1-olefin include 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and 1-docosene.
  • the alcohol represented by the above general formula (2) is preferably an addition product of the above 1-olefin and ethylene glycol.
  • the 1-olefin may be one type, or two or more types may be appropriately mixed.
  • the 1-olefin is preferably 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, or 1-docosene having 8 to 22 carbon atoms, more preferably 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or 1-eicosene having 10 to 20 carbon atoms in total, and even more preferably 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene having 12 to 18 carbon atoms.
  • n has a distribution of 1 to 3.
  • the repeating unit n of the ethylene glycol chain is the number of moles added, which is 1 to 3.
  • n is preferably 1 to 2, and more preferably 1 to 1.5.
  • the alcohol represented by the above general formula (2) is not particularly limited, but specific examples include 2-[(1-methylpentyl)oxy]ethanol, 2-[(1-methylhexyl)oxy]ethanol, 2-[(1-methylheptyl)oxy]ethanol, 2-[(1-methyloctyl)oxy]ethanol, 2-[(1-methylnonyl)oxy]ethanol, 2-[(1-methyldecyl)oxy]ethanol, 2-[(1-methylundecyl)oxy]ethanol, 2-[(1-methyldodecyl)oxy]ethanol, )oxy]ethanol, 2-[(1-methyltridecyl)oxy]ethanol, 2-[(1-methyltetradecyl)oxy]ethanol, 2-[(1-methylpentadecyl)oxy]ethanol, 2-[(1-methylhexadecyl)oxy]ethanol, 2-[(1-methylheptadecyl)oxy]ethanol, 2-[(1-methyloctadecyl)oxy]ethanol,
  • the (meth)acrylate of the present invention can be obtained by esterifying an alcohol represented by the following general formula (2) (hereinafter the same) with (meth)acrylic acid.
  • (meth)acrylic acid a toluene solvent, an acid catalyst, and a polymerization inhibitor were charged as in the case of normal esterification in the synthesis of (meth)acrylate, and the reaction was carried out at 80° C. while refluxing the toluene solvent in the presence of an oxygen-containing gas, a runaway polymerization reaction occurred immediately after the start of the reaction.
  • the inventors have found that the cause of this runaway polymerization reaction lies in the raw material alcohol of general formula (2), and have also found that the runaway polymerization can be suppressed by carrying out a pretreatment for the esterification, namely, a heat treatment in the presence of an alcohol and a polymerization inhibitor, and then adding (meth)acrylic acid and an acid catalyst to carry out the esterification.
  • a pretreatment for the esterification namely, a heat treatment in the presence of an alcohol and a polymerization inhibitor
  • the heat treatment may be performed without a solvent, but can be performed in the presence of a solvent.
  • the solvent is preferably selected from the solvents to be used in the subsequent esterification.
  • esterification a solvent that forms an azeotrope with water and forms two liquid phases with water is preferred, and benzene, toluene, xylene, hexane, heptane, octane, and cyclohexane are more preferred.
  • the heat treatment is preferably carried out at a temperature within a range of 25° C. to 100° C.
  • the heat treatment is preferably carried out for 10 minutes to 120 hours.
  • the heat treatment is carried out at a temperature in the range of 25° C. to 100° C. for 10 minutes to 120 hours. More preferably, the heat treatment is carried out at a temperature in the range of 40° C. to 90° C. for 30 minutes to 50 hours, and even more preferably, at a temperature in the range of 50° C. to 80° C. for 60 minutes to 20 hours.
  • polymerization inhibitor examples include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroquinone, and the like.
  • quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol
  • alkylphenol-based polymerization inhibitors such as 2,6-di
  • amine-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, and 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine;
  • N-oxyl-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl.
  • At least one selected from hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl is preferred, and hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl are more preferred.
  • At least one polymerization inhibitor selected from the group consisting of quinone-based polymerization inhibitors, alkylphenol-based polymerization inhibitors, amine-based polymerization inhibitors, N-oxyl-based polymerization inhibitors, and phenothiazine is used as the polymerization inhibitor.
  • the amount of the polymerization inhibitor used is 10 ppm by weight to 10% by weight, preferably 100 ppm by weight to 5% by weight, more preferably 200 ppm by weight to 1% by weight, and even more preferably 500 ppm by weight to 0.5% by weight, based on 100% by weight of the alcohol represented by the above general formula (2).
  • An oxygen-containing gas may be bubbled in during the heat treatment.
  • (meth)acrylic acid and an esterification catalyst are added to carry out esterification.
  • the amount of (meth)acrylic acid is 0.5 to 5 equivalents, preferably 0.8 to 2 equivalents, more preferably 1 to 1.5 equivalents, relative to the alcohol.
  • the esterification catalyst may be a known acid catalyst, and examples of the acid catalysts that are generally used include hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, strongly acidic ion exchange resins, heteropolyacids such as phosphotungstic acid, and metal oxides.
  • Preferred are sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, and strongly acidic ion exchange resins.
  • the amount of the acid catalyst is 0.001 mol% to 50 mol% relative to the (meth)acrylic acid, preferably 0.01 mol% to 10 mol%, and more preferably 0.1 mol% to 5 mol%.
  • a polymerization inhibitor may be added. Also, an oxygen-containing gas may be blown into the reaction liquid.
  • the esterification reaction is a dehydration reaction, it is preferable to carry out the reaction in the presence of a solvent that forms an azeotrope with water while removing water from the system.
  • the reaction temperature is preferably 50°C to 120°C. If the temperature is lower than 50°C, the reaction time will be longer, and if the temperature exceeds 120°C, the possibility of runaway polymerization increases. In order to achieve this reaction temperature, it is preferable to appropriately increase or decrease the pressure in the reaction system.
  • the desired secondary (meth)acrylate compound can be obtained by purifying it using standard methods such as washing with alkaline water, washing with water, drying, and removing the solvent. Distillation may also be used as an alternative purification method.
  • the (meth)acrylate of the present invention can be obtained by transesterifying an alcohol represented by the general formula (2) with a (meth)acrylic acid ester (alkyl (meth)acrylate) represented by the above general formula (3).
  • a (meth)acrylate, a solvent, a transesterification catalyst, and a polymerization inhibitor are charged and the reaction is carried out at 80° C. while refluxing the solvent in the presence of an oxygen-containing gas, as in the transesterification reaction in the synthesis of a normal (meth)acrylate, a runaway polymerization reaction occurs immediately after the start of the reaction.
  • the inventors have found that the cause of this runaway polymerization reaction lies in the raw material alcohol of general formula (2), and have also discovered that the runaway polymerization can be suppressed by carrying out a pretreatment for the transesterification reaction, namely, by carrying out a heat treatment in the presence of an alcohol and a polymerization inhibitor, and then adding an alkyl (meth)acrylate and an ester catalyst to carry out esterification.
  • the heat treatment may be performed without a solvent, but can be performed in the presence of a solvent, and the solvent is preferably selected from the solvents used in the subsequent transesterification reaction.
  • the transesterification reaction is preferably performed using a solvent that discharges the alkyl alcohol by-produced from the alkyl (meth)acrylate out of the system, and hexane, heptane, octane, cyclohexane, etc. are preferably used.
  • the alkyl (meth)acrylate forms an azeotropic composition with the by-produced alcohol, a method of discharging it out of the system using the alkyl (meth)acrylate as a solvent can also be adopted.
  • alkyl (meth)acrylate examples include (meth)acrylates having a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms. Among these, (meth)acrylates having an alkyl group having 1 to 4 carbon atoms are preferably used.
  • alkyl (meth)acrylates include the following compounds: (meth)acrylic acid lower alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate. These can be used alone or in combination.
  • (meth)acrylic acid lower alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate.
  • the heat treatment is preferably carried out for 10 minutes to 120 hours.
  • the heat treatment is also preferably carried out at a temperature in the range of 25°C to 100°C. More preferably, the heat treatment is carried out at a temperature in the range of 25°C to 100°C for 10 minutes to 120 hours, even more preferably at a temperature in the range of 40°C to 90°C for 30 minutes to 50 hours, and even more preferably at a temperature in the range of 50°C to 80°C for 60 minutes to 20 hours.
  • the above-mentioned polymerization inhibitors include, for example, quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydro amine-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-t
  • At least one selected from hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl is preferred, with hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl being more preferred.
  • the amount of the polymerization inhibitor used is 10 ppm by weight to 10% by weight, preferably in the range of 100 ppm by weight to 5% by weight, more preferably in the range of 200 ppm by weight to 1% by weight, and even more preferably in the range of 500 ppm by weight to 0.5% by weight, based on 100% by weight of the polyethylene glycol mono-higher alkyl ether.
  • An oxygen-containing gas may be bubbled in during the heat treatment.
  • an alkyl (meth)acrylate and an ester exchange catalyst are added to carry out an ester exchange reaction.
  • the alkyl (meth)acrylate is the alkyl (meth)acrylate described above, and the amount is 0.5 to 5 equivalents, preferably 0.8 to 2 equivalents, more preferably 1 to 1.5 equivalents, relative to the alcohol.
  • the alkyl (meth)acrylate is used as an excluding solvent for the by-produced alcohol, it may be further added.
  • a known catalyst may be used for the ester exchange, and the catalyst is not particularly limited, but specific examples thereof include oxides such as calcium oxide, barium oxide, lead oxide, zinc oxide, and zirconium oxide; hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, thallium hydroxide, tin hydroxide, lead hydroxide, and nickel hydroxide; halides such as lithium chloride, calcium chloride, tin chloride, lead chloride, zirconium chloride, and nickel chloride; carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, lead carbonate, zinc carbonate, and nickel carbonate; hydrogen carbonates such as potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate; phosphates such as sodium phosphate, potassium phosphate, rubidium phosphate, lead phosphate, zinc phosphate, and nickel phosphate; nitrates such as lithium nitrate, calcium nitrate, lead nitrate
  • alkoxy compounds include lithium t-butoxide, calcium methoxide, calcium ethoxide, barium methoxide, barium ethoxide, tetraethoxytitanium, tetrabutoxytitanium, tetraisopropoxytitanate, and tetra(2-ethylhexanoxy)titanium; acetylacetonate complexes such as lithium acetylacetonate, zirconia acetylacetonate, zinc acetylacetonate, dibutoxytin acetylacetonate, and dibutoxytitanium acetylacetonate; quaternary ammonium alkoxides such as tetramethylammonium methoxide, tetramethylammonium t-butoxide, and trimethylbenzylammonium ethoxide; dialkyltin compounds such as dimethyltin oxide, methylbutylt
  • the amount of the transesterification catalyst used is not particularly limited, but specifically, relative to the alcohol represented by general formula (2), it is preferably 0.001 mol% or more, more preferably 0.005 mol% or more, even more preferably 0.01 mol% or more, particularly preferably 0.05 mol% or more, preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less.
  • the above range of the transesterification catalyst amount is preferable in terms of yield and economy.
  • a polymerization inhibitor may be added. Also, an oxygen-containing gas may be blown into the reaction liquid.
  • the reaction temperature is preferably 50°C to 120°C. If the temperature is lower than 50°C, the reaction time will be longer, and if the temperature exceeds 120°C, the possibility of runaway polymerization increases. In order to achieve this reaction temperature, it is preferable to appropriately increase or decrease the pressure in the reaction system.
  • the target secondary (meth)acrylate compound can be obtained by purifying the product by a conventional method such as acid washing, water washing, filtration, drying, and solvent removal. As another purification method, distillation may be used.
  • the (meth)acrylate of the present invention is a (meth)acrylate represented by general formula (1) and has a carbon-carbon double bond, so that it can be used as a monomer to obtain a polymer.
  • the polymer may be composed of structural units derived from the (meth)acrylate of the present invention, but may also contain other structural units.
  • the polymer may contain 0.1 to 100 mol % of structural units derived from the (meth)acrylate of the present invention based on the total structural units.
  • the proportion of structural units derived from the (meth)acrylate of the present invention is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, even more preferably 20 to 100 mol%, still more preferably 25 to 100 mol%, still more preferably 30 to 100 mol%, still more preferably 50 to 100 mol%, and particularly preferably 70 to 100 mol%.
  • Copolymerizable monomers include alkyl acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, and octadecyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate, and methoxydiethylene glycol (meth)acrylate.
  • alkyl acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-e
  • alkyl polyoxyalkyl (meth)acrylates such as methoxypropylene glycol (meth)acrylate, ethoxypropylene glycol (meth)acrylate, and methoxydipropylene glycol (meth)acrylate
  • hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate
  • carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid
  • ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and isobornyl
  • Silicon-containing monomers such as 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane, vinyl chloride, (meth)acrylates having an Rf group (a group in which two or more hydrogen atoms of an alkyl group are replaced with fluorine atoms) (the Rf group may contain halogen atoms other than fluorine atoms. The other halogen atoms are preferably chlorine atoms. Furthermore, an ether-type oxygen atom or a thioether-type sulfur atom may be inserted between the carbon-carbon bonds in the Rf group.) can be used as one or more of the copolymerizable monomers.
  • Rf group a group in which two or more hydrogen atoms of an alkyl group are replaced with fluorine atoms
  • the other halogen atoms are preferably chlorine atoms.
  • an ether-type oxygen atom or a thioether-type sulfur atom may be inserted between
  • polyether aliphatic urethane acrylate, polycarbonate urethane acrylate, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, isobornyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, and tricyclodecane dimethanol diacrylate can also be used as copolymerizable monomers.
  • the weight average molecular weight of the polymer in the present invention is preferably, for example, 1,000 to 10,000,000 as determined by the static light scattering method.
  • the glass transition temperature of the polymer in the present invention is desirably, for example, ⁇ 40° C. or higher.
  • the upper limit of the glass transition temperature of the polymer of the present disclosure is desirably, for example, 80° C. or lower.
  • the glass transition temperature is calculated by using the glass transition temperature of a homopolymer of the monomer used in the monomer component constituting the polymer.
  • Formula (I): 1/Tg ⁇ (Wm/Tgm)/100 (I)
  • Wm is the content (mass%) of monomer m in the monomer components constituting the polymer
  • Tgm is the glass transition temperature (absolute temperature: K) of a homopolymer of monomer m.
  • the polymerization to obtain the polymer of the present invention is expected to be carried out in the presence of a polymerization initiator.
  • the polymerization initiator include azo compounds such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane)hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine); persulfates such as potassium persulfate; and peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
  • the polymerization initiators may be used alone or in combination of two or more.
  • the amount of polymerization initiator used may be appropriately set depending on the type of polymerization initiator, etc., and is not particularly limited, but may be, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and may be, for example, 2 parts by mass or less, preferably 1 part by mass or less, relative to 100 parts by mass of the monomer component.
  • additives such as a chain transfer agent may be included in the reaction system. Any appropriate additive may be used as the additive.
  • additives such as mercaptoethanol, thioglycolic acid, and sodium disulfite may be added during polymerization.
  • the polymerization reaction may be carried out in the presence of a reducing agent (e.g., sodium hydrogen sulfite), a decomposing agent for the polymerization initiator (e.g., a transition metal salt such as ferrous sulfate), a chain transfer agent [e.g., a compound having a thiol group (e.g., tert-dodecyl mercaptan)], a pH buffer, a chelating agent, etc., as necessary.
  • a reducing agent e.g., sodium hydrogen sulfite
  • a decomposing agent for the polymerization initiator e.g., a transition metal salt such as ferrous sulfate
  • a chain transfer agent e.g., a compound having a thiol group (e.g., tert-dodecyl mercaptan)]
  • a pH buffer e.g., a chelating agent, etc.
  • a method can be employed in which a (meth)acrylate is added to a polymer having a functional group having an active hydrogen capable of being added to an olefin.
  • a method of adding a (meth)acrylate to a polymer having a primary or secondary amino group in the molecule a method of adding a (meth)acrylate to a polymer having a thiol group in the molecule, a reaction with a polymer having a hydroxyl group in the molecule, etc. can be used.
  • the polymers having active hydrogen may be used alone or in combination of two or more kinds.
  • the amount of (meth)acrylate used relative to the active hydrogen-containing polymer may be appropriately set depending on the number of active hydrogen groups contained, and is not particularly limited. However, the amount of (meth)acrylate relative to the active hydrogen group equivalent may be, for example, 0.1 to 100 equivalents, preferably 0.5 to 80 equivalents.
  • the addition of active hydrogen groups is a reaction known as Michael addition, and although a catalyst does not have to be used, it is acceptable to use one. Any known catalyst can be used.
  • the compound of the present invention can be used, for example, as a water/oil repellent for textile products.
  • the present invention also relates to a water/oil repellent comprising a polymer containing a structural unit derived from the (meth)acrylate of the present invention.
  • the water/oil repellent can be used by applying it to a substrate.
  • a polymer can be synthesized in advance using the (meth)acrylate compound of the present invention as a monomer, and a water/oil repellent containing the polymer can be applied.
  • a functional group that reacts with urethane resin, epoxy resin, etc. such as a hydroxyl group, a carboxyl group, or a silanol group, is provided to the polymer chain, and crosslinking is formed and cured to form a coating layer, which imparts water/oil repellency to the substrate.
  • the substrate is not particularly limited, but examples thereof include fibers and films.
  • the present invention is also a method for imparting water and oil repellency to a substrate, comprising the step of adhering a polymer to the substrate.
  • the step of attaching the polymer is preferably carried out by coating the polymer on the substrate.
  • the method for imparting water and oil repellency to a substrate preferably includes a step of forming a coating layer by introducing crosslinks between the polymers after the polymer adhesion step.
  • the present invention also relates to a method for producing a water- and oil-repellent substrate, the method comprising the steps of: applying a polymer containing a structural unit derived from the (meth)acrylate of the present invention onto a substrate; and, after the step of applying the polymer, introducing crosslinks between the polymers to form a coating layer.
  • a solution of the polymer diluted with water or a solvent onto the substrate it is preferable to apply a solution of the polymer diluted with water or a solvent onto the substrate by spraying.
  • the compound of the present invention can be used, for example, as ink, paint, pressure sensitive adhesive, adhesive, UV curable resin diluent, water/oil repellent, etc., and is preferably used as a water/oil repellent.
  • the water/oil repellent can be used by applying it to a substrate.
  • a polymer can be synthesized in advance using the compound of the present invention as a monomer, and a water/oil repellent containing the polymer can be applied.
  • the polymer chain is provided with a functional group that reacts with urethane resin, epoxy resin, etc., such as a hydroxyl group, a carboxyl group, or a silanol group, and crosslinked to form a coating layer that is cured to impart water/oil repellency to the substrate.
  • a functional group that reacts with urethane resin, epoxy resin, etc. such as a hydroxyl group, a carboxyl group, or a silanol group
  • the compound of the present invention is expected to be used as an adhesive or sealing material for electronic components or semiconductor elements, a raw material for a constituent material of a film or prepreg, an ink for 3D printing, a quantum dot ink, an adhesive such as a UV-curable lamination adhesive or a UV-curable hot melt adhesive, a sealant, or the like.
  • reaction liquid was cooled to room temperature, the upper dodecene phase was separated, and unreacted dodecene was distilled off, and then 155 g of an isomer mixture of secondary dodecanol monoethoxylate (alcohol (1)) was obtained at a boiling point range of 129 to 131°C (temperature at the top of the distillation tower; the same applies below) at a reduced pressure of 2 mmHg.
  • the secondary dodecanol monoethoxylate (1) contained 0.3% by mass of MEG and MEG polymers.
  • 900 g (14.52 mol) of monoethylene glycol (MEG), and BEA-type zeolite (trade name: VALFOR CP811 BL-25) manufactured by PQ Corporation as a catalyst were added.
  • BL-25 100g was charged into a 3000ml glass reactor equipped with a stirring blade and a reflux condenser, the gas phase was replaced with nitrogen, and then the mixture was maintained in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150°C while stirring at a rotation speed of 600 rpm, and the mixture was reacted at the same temperature for 3 hours. Thereafter, the reaction liquid was cooled to room temperature, and the upper tetradecene phase was separated.
  • MEG monoethylene glycol
  • BEA-type zeolite trade name: VALFOR CP811 BL-25
  • Example 1 ⁇ Direct esterification with acrylic acid>
  • a thermometer a thermometer
  • a stirrer a condenser
  • a gas inlet tube a gas inlet tube
  • 139 g a thermometer
  • a stirrer a condenser
  • a gas inlet tube a gas inlet tube
  • 100 g of toluene as an organic solvent 100 g
  • 0.14 g of phenothiazine (1000 ppm by weight relative to the alcohol) as a polymerization inhibitor were heated at 80° C. for 4 hours.
  • the upper organic layer was transferred to a four-necked flask equipped with a thermometer, a stirrer, a cooling tube, and a gas inlet tube, and heated under reduced pressure while blowing in 7% oxygen/nitrogen gas to distill off the toluene, obtaining 159 g of a product (2-[(1-methylundecyl)oxy]ethyl acrylate isomer mixture).
  • the purity of this acrylate product was 98%, and it contained unreacted alcohol.
  • This product was stored in a refrigerator at -20°C for 70 hours, but no crystal precipitation was observed.
  • the H-NMR of the product was measured, and the NMR chart is shown in FIG.
  • Example 1 In the production method described in Example 1, the contents were charged into a flask all at once and the esterification reaction was carried out without the heat treatment at 80° C. for 4 hours. After about 1 hour, the formation of a polymer of acrylic acid was observed.
  • Example 2 ⁇ Transesterification reaction with methyl acrylate>
  • 164 g (0.63 mol) of the alcohol (2) synthesized in Synthesis Example 2 and 0.16 g (1000 ppm by weight relative to the alcohol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a polymerization inhibitor were charged, and the mixture was heated at 80° C. for 4 hours with stirring.
  • 273 g (3.17 mol) of methyl acrylate and 9.0 g of tetraisopropoxy titanate as a catalyst were charged and heated with stirring.
  • Example 2 In the production method described in Example 2, the contents were charged into a flask all at once to carry out the transesterification reaction without the heat treatment at 80° C. for 4 hours. After about 1 hour, the reaction liquid was found to have thickened, and a polymer of methyl acrylate was formed.
  • Example 3 Into a four-neck flask equipped with a thermometer, a stirrer, a cooling tube, and a gas inlet tube, 164 g (0.57 mol) of the alcohol (3) synthesized in Synthesis Example 3, 100 g of toluene as an organic solvent, and 0.82 g of phenothiazine (5,000 ppm by weight relative to the alcohol) as a polymerization inhibitor were charged, and the mixture was heated at 40° C. for 80 hours with stirring.
  • the upper organic layer was transferred to a four-necked flask equipped with a thermometer, a stirrer, a cooling tube, and a gas inlet tube, and heated under reduced pressure while blowing in 7% oxygen/nitrogen gas to distill off the toluene, obtaining 190 g of a product (2-[(1-methylpentadecyl)oxy]ethyl acrylate) isomer mixture.
  • the purity of this acrylate product was 96%, and it contained unreacted alcohol.
  • this product was stored in a refrigerator at -20°C for 10 hours, it crystallized, but no crystal precipitation was observed at -5°C. It has been shown that it is possible to obtain the compounds of the present invention by the processes described in Examples 1 to 3 above.
  • Example 4 20 g of the (meth)acrylate synthesized in Example 3, 100 g of dioxane as an organic solvent, and 0.4 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were added to a four-neck flask equipped with a thermometer, a stirrer, a cooling tube, and a gas inlet tube, and polymerization was carried out at 70° C. After polymerization for 2 hours, the reaction solution had become viscous, and the production of a polymer was confirmed. The produced polymer was subjected to NMR measurement, and it was found to contain 2% of unpolymerized components.
  • V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Example 5 In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 20 parts of the acrylate synthesized in Example 4 was heated and melted, and 1 part of a nonionic surfactant (product name "Noigen ES-149D", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 63 parts of warm water (60°C) were mixed and emulsified using a high-pressure emulsifier to prepare an aqueous dispersion (emulsion) with a nonvolatile content of 25%.
  • a nonionic surfactant product name "Noigen ES-149D", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • aqueous dispersion 20 parts of this aqueous dispersion was mixed with 5 parts of polyethyleneimine (product name "Epomin (registered trademark) HM-2000", manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 30,000) to prepare an aqueous dispersion (water repellent composition) having a non-volatile content of 25%.
  • the water repellent composition was diluted 25 times with water, and a polyester fabric (Polyester Tropical, manufactured by Teijin Co., Ltd.) was immersed in the diluted water repellent composition.
  • the polyester fabric to which the water repellent composition was applied was dried in a dryer at 180°C for 5 minutes to obtain a water repellent fiber.
  • the amount of the water repellent composition applied to the polyester fabric was 1.3 g/ m2 .
  • the obtained fiber was tested according to the spray method of JIS L 1092 (2009) at a shower water temperature of 20° C. The results were evaluated visually and showed that some adhesion and wetness was present on the surface, but other areas were not.
  • Example 1 The same procedure as in Example 5 was carried out except that 20 parts of stearyl acrylate was used in place of 20 parts of the acrylate synthesized in Example 4, to obtain a reference polyester fiber.
  • the obtained fiber was tested according to the spray method of JIS L 1092 (2009) with shower water at a temperature of 20° C. The results were evaluated visually, and the surface was wetted, but no water droplets were observed.
  • Example 5 The evaluation of Example 5 above demonstrated that the (meth)acrylate of the present invention has a water-repellent effect.

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Abstract

Le but de la présente invention est de fournir : une composition qui contient un nouveau composé ayant d'excellentes propriétés de manipulation ; et un procédé de production, une utilisation ou similaire de cette composition. La présente invention concerne une composition contenant du (méth)acrylate qui contient au moins deux isomères d'un (méth)acrylate qui est représenté par la formule générale (1) (dans laquelle R1 représente un atome d'hydrogène ou un groupe méthyle ; R2 et R3 représentent chacun un groupe alkyle ; le nombre total d'atomes de carbone dans R2 et R3 est de 6 à 22 ; et n représente un nombre de 1 à 3). Cette composition contenant du (méth)acrylate contient (A) l'isomère dans lequel R2 est un groupe méthyle et (B) l'isomère dans lequel R2 est un groupe alkyle ayant 2 atomes de carbone ou plus.
PCT/JP2023/038309 2022-10-24 2023-10-24 Composition contenant un (méth)acrylate WO2024090423A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064386A1 (fr) * 1998-06-05 1999-12-16 Nippon Shokubai Co., Ltd. Composition de derives d'ether d'alkyle superieur de polyalkylene glycol, detergent, lubrifiant et preparation a usage externe pour la peau contenant chacun cette composition
JP2011513275A (ja) * 2008-02-27 2011-04-28 ビーエーエスエフ ソシエタス・ヨーロピア Ｃ１０−アルコール混合物の（メタ）アクリラートの製造方法
WO2015076347A1 (fr) * 2013-11-22 2015-05-28 ダイキン工業株式会社 Agent de traitement de surface de type émulsion aqueuse
WO2021049492A1 (fr) * 2019-09-09 2021-03-18 株式会社日本触媒 Précurseur d'alcoxylate d'alcool secondaire supérieur, produit d'addition d'alcoxylate d'alcool secondaire supérieur, et sel d'ester d'acide sulfurique d'éther d'alkyle secondaire supérieur, et leurs procédés de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064386A1 (fr) * 1998-06-05 1999-12-16 Nippon Shokubai Co., Ltd. Composition de derives d'ether d'alkyle superieur de polyalkylene glycol, detergent, lubrifiant et preparation a usage externe pour la peau contenant chacun cette composition
JP2011513275A (ja) * 2008-02-27 2011-04-28 ビーエーエスエフ ソシエタス・ヨーロピア Ｃ１０−アルコール混合物の（メタ）アクリラートの製造方法
WO2015076347A1 (fr) * 2013-11-22 2015-05-28 ダイキン工業株式会社 Agent de traitement de surface de type émulsion aqueuse
WO2021049492A1 (fr) * 2019-09-09 2021-03-18 株式会社日本触媒 Précurseur d'alcoxylate d'alcool secondaire supérieur, produit d'addition d'alcoxylate d'alcool secondaire supérieur, et sel d'ester d'acide sulfurique d'éther d'alkyle secondaire supérieur, et leurs procédés de production

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