Composition containing ester compound, method for producing same, polymerizable composition, and method for producing (meth) acrylic polymer

Abstract

The purpose of the present invention is to provide an ester compound-containing composition having excellent storage stability, a method for producing the same, a polymerizable composition using the ester compound-containing composition, and a method for producing a (meth) acrylic polymer. The composition containing an ester compound contains a compound represented by formula (1) CH2 = CR1-C (= O)-O-R2 (wherein R1 represents a hydrogen atom or a methyl group; r2 represents a C2-20 hydrocarbon group, a C2-8 linear or branched alkyl group in which at least one hydrogen atom is substituted by a hydroxyl group, a C2-8 linear or branched alkyl group in which one or two hydrogen atoms are substituted by a (meth) acryloyloxy group, or a group having an etheric oxygen group between carbon atoms of a C2-8 hydrocarbon group. And a component A, i.e., an alpha-olefin, the content of the component A being 1-1500 ppm by mass, and the water content being 5000 ppm by mass or less.

Description

Technical Field

[0001] The present invention relates to a composition containing an ester compound and a method for producing the same, a polymerizable composition, and a method for producing a (meth)acrylic acid-based polymer.

[0002] This application claims priority based on Japanese Patent Application No. 2022-149219, Japanese Patent Application No. 2022-149220, and Japanese Patent Application No. 2022-149221 filed in Japan on September 20, 2022, and the contents of which are incorporated herein by reference. Background Art

[0003] (Meth)acrylic acid-based polymers obtained using (meth)acrylates are used in various fields such as coatings, adhesives, resin modifiers, artificial marbles, and paper latex.

[0004] As a method for producing (meth)acrylate, for example, the following method is known: a raw material (meth)acrylate alkyl ester is subjected to an ester exchange reaction with an alkyl alcohol in the presence of Ti(OR)4 (R is an alkyl group) as a catalyst to produce a target (meth)acrylate alkyl ester (for example, Patent Document 1).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2009-274986 Summary of the invention

[0008] If the ester compound-containing composition containing (meth)acrylate is stored for a certain period of time after production, the quality of the ester compound-containing composition may be deteriorated.

[0009] An object of the present invention is to provide an ester compound-containing composition having excellent storage stability, a method for producing the same, a polymerizable composition using the ester compound-containing composition, and a method for producing a (meth)acrylic polymer.

[0010] The present inventors have conducted intensive research and found that during storage of a composition containing an ester compound, the concentration of a pure component decreases due to the generation of impurities such as (meth)acrylate dimers. Impurities such as (meth)acrylate dimers may be an important factor that causes the physical properties of (meth)acrylic polymers to decrease.

[0011] The present inventors conducted further studies and found that the composition containing an ester compound contains specific components to suppress the generation of impurities such as dimers of (meth)acrylate and improve the storage stability, thereby completing the present invention.

[0012] That is, the present invention includes the following aspects.

[0013] [1] An ester compound-containing composition comprising an ester compound (1) represented by the following formula (1) and an α-olefin as component A,

[0014] The content of the component A is 1 ppm to 1500 ppm by mass.

[0015] The water content is 5000 mass ppm or less.

[0016] CH2=CR 1 -C(=O)-O-R 2 ···(1)

[0017] (Wherein, in the above formula (1), R 1 is a hydrogen atom or a methyl group, R 2 It is a hydrocarbon group having 2 to 20 carbon atoms which may have a hetero atom and may have a functional group.

[0018] [2] The composition containing an ester compound according to [1], wherein in the above formula (1), R 2 A hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxyl group, a linear or branched alkyl group having 2 to 8 carbon atoms or a group in which one or two hydrogen atoms of a hydroxyalkyl group are substituted with a (meth)acryloyloxy group, or a group having an ethereal oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[0019] [3] The ester compound-containing composition according to [1], wherein the ester compound (1) comprises an ester compound (1-1) represented by the following formula (1-1).

[0020] CH2=CR a1 -C(=O)-O-R a2 ···(1-1)

[0021] (Wherein, in the above formula (1-1), R a1 is a hydrogen atom or a methyl group, R a2 It is a hydrocarbon group having 2 to 20 carbon atoms.

[0022] [4] The composition containing an ester compound according to [3], comprising the above R a2 The above-mentioned ester compound (1-1) is a linear or branched alkyl group having 2 to 20 carbon atoms.

[0023] [5] The composition containing an ester compound according to [3] or [4], wherein the content of the ester compound (1-1) is 85.00% by mass to 99.99% by mass.

[0024] [6] A composition containing an ester compound according to any one of [1] to [5], wherein the ester compound (1) comprises one or more ester compounds (1-2) selected from the group consisting of an ester compound (1-21) represented by the following formula (1-21), an ester compound (1-22) represented by the following formula (1-22), and an ester compound (1-23) represented by the following formula (1-23).

[0025]

[0026] (Wherein, in the above formulas (1-21) to (1-23), R b1 , R b3 , R b5 , R b6 , R b8 and R b9 are each independently a hydrogen atom or a methyl group, R b2 and R b4 are each independently a linear or branched alkylene or hydroxyalkylene group having 2 to 8 carbon atoms, R b7 It is a straight-chain or branched trivalent hydrocarbon group having 2 to 8 carbon atoms.

[0027] [7] The composition containing an ester compound according to [6], wherein the ester compound (1-2) comprises one or more selected from ethylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and trimethylolpropane tri(meth)acrylate.

[0028] [8] The composition containing an ester compound according to [6] or [7], wherein the content of the ester compound (1-2) is 85.00% by mass to 99.99% by mass.

[0029] [9] The composition containing an ester compound according to any one of [1] to [8], wherein the ester compound (1) comprises an ester compound (1-3) represented by the following formula (1-3).

[0030] CH2=CR c1 -C(=O)-O-R c2 ···(1-3)

[0031] (Wherein, in the above formula (1-3), R c1 is a hydrogen atom or a methyl group, R c2 A group having an ethereal oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[0032]

[10] The composition containing an ester compound according to [9], comprising the above-mentioned R c2The ester compound (1-3) is 2-methoxyethyl, glycidyl or tetrahydrofurfuryl.

[0033]

[11] The composition containing an ester compound according to [9] or

[10] , wherein the content of the ester compound (1-3) is 85.00% by mass to 99.99% by mass.

[0034]

[12] The ester compound-containing composition according to any one of [1] to

[11] , wherein the component A contains an α-olefin having 6 to 12 carbon atoms.

[0035]

[13] The composition containing an ester compound according to any one of [1] to

[12] , further comprising a polymerization inhibitor as component B.

[0036]

[14] The composition containing an ester compound according to any one of [1] to

[13] , which is a composition containing an ester compound that can be stored for one day or more.

[0037]

[15] A method for producing a composition containing an ester compound, the composition containing an ester compound comprising an ester compound (1) represented by the following formula (1),

[0038] The production method comprises the step of conducting an ester exchange reaction between methyl (meth)acrylate and an alcohol (a) having 2 to 20 carbon atoms in the presence of an α-olefin which is component A.

[0039] CH2=CR 1 -C(=O)-O-R 2 ···(1)

[0040] (Wherein, in the above formula (1), R 1 is a hydrogen atom or a methyl group, R 2 It is a hydrocarbon group having 2 to 20 carbon atoms which may have a hetero atom and may have a functional group.

[0041]

[16] The method for producing a composition containing an ester compound according to

[15] , wherein in the above formula (1), R 2 a hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxyl group, a linear or branched alkyl group having 2 to 8 carbon atoms or a group in which one or two hydrogen atoms of a hydroxyalkyl group are substituted with a (meth)acryloyloxy group, or a group having an ethereal oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms,

[0042] The alcohol (a) is at least one selected from the following alcohols (a1) to (a3).

[0043] (a1) Monohydric alcohol having 2 to 20 carbon atoms

[0044] (a2) at least one alcohol selected from diols having 2 to 8 carbon atoms and triols having 2 to 8 carbon atoms

[0045] (a3) Alcohols having 2 to 8 carbon atoms and containing an ether bond

[0046]

[17] The method for producing a composition containing an ester compound according to

[16] , wherein an ester compound (1-1) represented by the following formula (1-1) is obtained by performing an ester exchange reaction between methyl (meth)acrylate and the alcohol (a1) in the presence of the component A.

[0047] CH2=CR a1 -C(=O)-O-R a2 ···(1-1)

[0048] (Wherein, in the above formula (1-1), R a1 is a hydrogen atom or a methyl group, R a2 It is a hydrocarbon group having 2 to 20 carbon atoms.

[0049]

[18] The method for producing a composition containing an ester compound according to

[17] , wherein the alcohol (a1) comprises a linear or branched monohydric alcohol having 2 to 20 carbon atoms.

[0050]

[19] A method for producing a composition containing an ester compound according to any one of

[15] to

[18] , wherein an ester exchange reaction is carried out between methyl (meth)acrylate and the alcohol (a2) in the presence of the component A to obtain an ester compound (1-2) comprising one or more ester compounds (1-2) selected from the group consisting of an ester compound (1-21) represented by the following formula (1-21), an ester compound (1-22) represented by the following formula (1-22), and an ester compound (1-23) represented by the following formula (1-23).

[0051]

[0052] (In the above formulas (2-1) to (2-3), R b1 , R b3 , R b5 , R b6 , R b8 and R b9 are each independently a hydrogen atom or a methyl group, R b2 and R b4 are each independently a linear or branched alkylene or hydroxyalkylene group having 2 to 8 carbon atoms, R b7 It is a straight-chain or branched trivalent hydrocarbon group having 2 to 8 carbon atoms.

[0053]

[20] The method for producing a composition containing an ester compound according to

[19] , wherein the alcohol (a2) comprises one or more selected from ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and trimethylolpropane.

[0054]

[21] The method for producing a composition containing an ester compound according to any one of

[15] to

[20] , wherein an ester compound (1-3) represented by the following formula (1-3) is obtained by carrying out an ester exchange reaction between methyl (meth)acrylate and the alcohol (a3) ​​in the presence of the component A.

[0055] CH2=CR c1 -C(=O)-O-R c2 ···(1-3)

[0056] (Wherein, in the above formula (1-3), R c1 is a hydrogen atom or a methyl group, R c2 A group having an ethereal oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[0057]

[22] The method for producing a composition containing an ester compound according to

[21] , wherein the alcohol (a3) ​​comprises one selected from the group consisting of 2-methoxyethanol, glycidyl alcohol, and tetrahydrofurfuryl alcohol.

[0058]

[23] The method for producing a composition containing an ester compound according to any one of

[15] to

[22] , wherein the component A contains an α-olefin having 6 to 12 carbon atoms.

[0059]

[24] A polymerizable composition for producing a (meth)acrylic polymer, comprising the composition containing an ester compound according to any one of [1] to

[14] .

[0060]

[25] The polymerizable composition according to

[24] , wherein the content of component C, i.e., at least one compound selected from compounds of transition metals and compounds of Group IIIA elements, is 7×10 4 Mass ppm or less.

[0061]

[26] A method for producing a (meth)acrylic polymer, comprising the step of polymerizing the polymerizable composition described in

[24] .

[0062]

[27] A method for producing a (meth)acrylic polymer, comprising the step of polymerizing the polymerizable composition described in

[25] .

[0063] According to the present invention, there can be provided an ester compound-containing composition having excellent storage stability, a method for producing the same, a polymerizable composition using the ester compound-containing composition, and a method for producing a (meth)acrylic polymer. DETAILED DESCRIPTION

[0064] The following terms in this specification and claims are defined as follows.

[0065] "Monomer" refers to a compound having a polymerizable carbon-carbon double bond.

[0066] "(Meth)acrylate" is selected from "acrylate" and "methacrylate".

[0067] "(Meth)acrylic acid" is selected from "acrylic acid" and "methacrylic acid".

[0068] The "α-olefin" refers to an olefin having a carbon-carbon double bond at the α position.

[0069] "Transition metals" refer to metal elements located in Group IIIB to Group IIB in the periodic table. Typically, they are scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), lanthanum (La), cerium (Ce) ), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), etc.

[0070] “Group IIIA elements” refer to elements in Group IIIA of the periodic table, typically boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl).

[0071] “Periodic Table” refers to “Periodic Table of Elements” (URL https: / / pubchem.ncbi.nlm.nih.gov / periodic-table / .

[0072] [Composition containing an ester compound]

[0073] The ester compound-containing composition according to one example of the embodiment of the present invention contains an ester compound (1) described below and an α-olefin which is component A.

[0074] (Ester compound (1))

[0075] The ester compound (1) is a (meth)acrylate represented by the following formula (1).

[0076] CH2=CR 1 -C(=O)-O-R 2 ···(1)

[0077] In the above formula (1), R 1 is a hydrogen atom or a methyl group, R 2 It is a hydrocarbon group having 2 to 20 carbon atoms which may have a hetero atom and may have a functional group.

[0078] As R 2 The optional hetero atom includes nitrogen, oxygen, phosphorus, sulfur and the like, and nitrogen and oxygen are preferred.

[0079] As R 2 The functional group that can be possessed includes hydroxyl group, aldehyde group, carbonyl group, carboxyl group, amino group, nitro group, nitroso group, thiol group, sulfonic acid group, fluoro group, chloro group, bromo group, iodo group and the like, and hydroxyl group, carbonyl group, carboxyl group, amino group, thiol group, sulfonic acid group, fluoro group, chloro group and bromo group are preferred.

[0080] As R 2 , preferably a hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxyl group, a linear or branched alkyl group having 2 to 8 carbon atoms or a group in which one or two hydrogen atoms of a hydroxyalkyl group are substituted with a (meth)acryloyloxy group, or a group having an ethereal oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[0081] The linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxyl group is preferably a linear or branched alkyl group having 2 to 8 carbon atoms in which one or two hydrogen atoms are substituted with a hydroxyl group.

[0082] The ester compound-containing composition according to one embodiment may contain an ester compound (1-1) represented by the following formula (1-1) as the ester compound (1). The ester compound (1-1) is R 2 A (meth)acrylate of a hydrocarbon group having 2 to 20 carbon atoms.

[0083] CH2=CR a1 -C(=O)-O-R a2 ···(1-1)

[0084] In the above formula (1-1), R a1 is a hydrogen atom or a methyl group. a2It is a hydrocarbon group having 2 to 20 carbon atoms.

[0085] R a2 The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

[0086] R a2 The hydrocarbon group may be linear or branched, or may have a ring. a2 When the hydrocarbon group has a ring, the ring may be an aliphatic ring or an aromatic ring.

[0087] R a2 The hydrocarbon group has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 2 to 12 carbon atoms.

[0088] As R a2 Examples of the hydrocarbon group include alkyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aromatic alkyl groups having 7 to 20 carbon atoms. The "aromatic alkyl group" refers to a group in which one or more hydrogen atoms of an alkyl group are substituted with an aryl group.

[0089] As R a2 Examples of the alkyl group include ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, lauryl, and stearyl.

[0090] As R a2 Examples of the cycloalkyl group include cyclopropyl, cyclohexyl and isobornyl.

[0091] As R a2 The alkenyl group includes, for example, a vinyl group and an allyl group.

[0092] As R a2 The cycloalkenyl group includes, for example, a cyclopentenyl group, a cyclopentadienyl group, and a cyclohexenyl group.

[0093] As R a2 The alkynyl group may, for example, be a propynyl group.

[0094] As R a2 The aryl group includes, for example, a phenyl group and a naphthyl group.

[0095] As R a2 The aromatic alkyl group may be, for example, a benzyl group.

[0096] From the viewpoint that the ester compound (1-1) is relatively easy to obtain and relatively easy to handle in terms of physical properties, R a2, preferably an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aromatic alkyl group having 7 to 20 carbon atoms, and more preferably an ethyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, lauryl group, cyclohexyl group, allyl group, phenyl group, or benzyl group.

[0097] Examples of the ester compound (1-1) include ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate.

[0098] As the ester compound (1-1), R is preferred because it is relatively easy to obtain and relatively easy to handle in terms of physical properties. a2 is a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 2 to 20 carbon atoms, R a2 is a cycloalkyl (meth)acrylate having a cycloalkyl group having 3 to 20 carbon atoms, R a2 is an alkenyl (meth)acrylate having an alkenyl group having 2 to 20 carbon atoms, R a2 is an aryl (meth)acrylate having an aryl group having 6 to 20 carbon atoms, R a2 The aromatic alkyl (meth)acrylate is an aromatic alkyl group having 7 to 20 carbon atoms, and more preferably ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate.

[0099] The ester compound (1-1) may be used alone or in combination of two or more.

[0100] The composition containing an ester compound according to one example of the embodiment may contain, as the ester compound (1), one or more ester compounds (1-2) selected from the group consisting of an ester compound (1-21) represented by the following formula (1-21), an ester compound (1-22) represented by the following formula (1-22), and an ester compound (1-23) represented by the following formula (1-23). 2 A (meth)acrylate in which at least one hydrogen atom is substituted with a hydroxyl group in a linear or branched alkyl group having 2 to 8 carbon atoms, or one or two hydrogen atoms of a linear or branched alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms are substituted with a (meth)acryloyloxy group.

[0101]

[0102] In the above formulas (1-21) to (1-23), R b1 , R b3 , R b5 , R b6 , R b8 and R b9 are each independently a hydrogen atom or a methyl group, R b2 and R b4 are each independently a linear or branched alkylene or hydroxyalkylene group having 2 to 8 carbon atoms, R b7 It is a linear or branched trivalent hydrocarbon group having 2 to 8 carbon atoms.

[0103] R b2 and R b4 The alkylene group or hydroxyalkylene group has 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms.

[0104] As R b2 and R b4 Examples of the alkylene group include ethylene, propylene, isopropylene and butylene.

[0105] As R b2 and R b4 Examples of the hydroxyalkylene group include a hydroxyethylene group, a hydroxypropylene group, and a hydroxybutylene group.

[0106] R b7 The trivalent hydrocarbon group has 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms.

[0107] As R b7 The trivalent hydrocarbon group may be, for example, -CH2-C(-CH2-)(-CH3)-CH2-.

[0108] Examples of the ester compound (1-21) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate.

[0109] Examples of the ester compound (1-22) include ethylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

[0110] Examples of the ester compound (1-23) include trimethylolpropane tri(meth)acrylate.

[0111] The ester compound (1-2) preferably contains at least one selected from ethylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and trimethylolpropane tri(meth)acrylate because of relatively easy availability.

[0112] The ester compound (1-2) may be used alone or in combination of two or more.

[0113] The composition containing an ester compound according to one embodiment may contain an ester compound (1-3) represented by the following formula (1-3) as the ester compound (1). The ester compound (1-3) is R 2 This is a (meth)acrylate having an etheric oxygen group between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[0114] CH2=CR c1 -C(=O)-O-R c2 ···(1-3)

[0115] In the above formula (1-3), R c1 is a hydrogen atom or a methyl group, R c2 A group having an etheric oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[0116] R c2 The number of etheric oxygen atoms in the hydrocarbon group is preferably one, but is not limited thereto and may be two or more.

[0117] R c2 The hydrocarbon group may be linear or branched, or may have a ring. c2 When the ring has a ring, the ring may or may not contain an etheric oxygen.

[0118] R c2 The hydrocarbon group has 2 to 8 carbon atoms, preferably 2 to 7 carbon atoms.

[0119] As R c2 Examples of the hydrocarbon group include 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, 2-[2-(2-methoxyethoxy)ethoxy]ethyl, glycidyl, and tetrahydrofurfuryl.

[0120] As R c2 , preferably 2-methoxyethyl, glycidyl or tetrahydrofurfuryl.

[0121] Examples of the ester compound (1-3) include 2-methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0122] As the ester compound (1-3), 2-methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate are preferred because they are relatively easy to handle in terms of physical properties.

[0123] The ester compound (1-3) may be used alone or in combination of two or more.

[0124] As the ester compound (1), only one selected from the ester compound (1-1), the ester compound (1-2) and the ester compound (1-3) may be used, or two or more of them may be used in combination.

[0125] (ingredient A)

[0126] By containing component A, the dimerization reaction of the ester compound (1) and the generation of oxidation products of the ester compound (1) during storage are suppressed, thereby providing an ester compound-containing composition having excellent storage stability. The reason for this is not clear, but is presumed as follows.

[0127] During storage of a composition containing an ester compound, free radicals derived from ultraviolet rays, such as hydroxyl radicals generated by absorption of ultraviolet rays from sunlight by oxygen molecules, are generated. Such free radicals may cause the generation of dimers of the ester compound (1) and the generation of oxidation products of the ester compound (1). It is speculated that since the coupling products of olefins to which free radicals generated by the action of ultraviolet rays are added are stable, the free radical scavenging effect is excellent. Therefore, it is speculated that the dimerization of the ester compound (1) based on the free radical polymerization mechanism and the generation of oxidation products are suppressed by capturing free radicals by α-olefins.

[0128] The α-olefin of component A is preferably a chain α-olefin. Component A preferably contains an α-olefin having 6 to 12 carbon atoms, and more preferably contains an α-olefin having 8 to 10 carbon atoms.

[0129] Examples of the α-olefin include 2-ethyl-1-hexene, 2-methyl-1-heptene, 4-methyl-1-heptene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene.

[0130] As component A, at least one selected from 2-ethyl-1-hexene, 1-octene and 1-dodecene is preferred, 1-octene or 1-dodecene is more preferred, and 1-octene is further preferred, because it is available at a relatively low cost.

[0131] The α-olefins may be used alone or in combination of two or more.

[0132] The ratio of the α-olefin having 6 to 12 carbon atoms to the total mass of component A is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, particularly preferably 99% by mass or more, and most preferably 100% by mass. The higher the ratio of the α-olefin having 6 to 12 carbon atoms, the more easily the effect of improving the storage stability of the composition containing the ester compound by the α-olefin can be obtained.

[0133] (ingredient B)

[0134] The ester compound-containing composition of the embodiment preferably further contains component B: a polymerization inhibitor in addition to the ester compound (1) and the α-olefin.

[0135] By containing a polymerization inhibitor, the polymerization reaction of the ester compound (1) based on the free radical polymerization mechanism during storage is suppressed. In addition, during storage, hydroxyl radicals may be generated due to the absorption of ultraviolet rays from sunlight by oxygen molecules in the composition containing the ester compound. However, since the polymerization inhibitor can capture hydroxyl radicals, the oxidation of the ester compound (1) by hydroxyl radicals is suppressed, and oxidation products are less likely to be generated.

[0136] Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, nitrobenzene compounds, nitroxide radical compounds, amine compounds, phosphorus-containing compounds, sulfur-containing compounds, iron-containing compounds, copper-containing compounds, and manganese-containing compounds. The polymerization inhibitor used may be one or more.

[0137] Examples of the phenolic compound include alkylphenols, hydroxyphenols, aminophenols, nitrophenols, nitrosophenols, alkoxyphenols, and tocopherols.

[0138] Examples of the alkylphenol include o-cresol, m-cresol, p-cresol, 2-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol, 2,2'-methylene-bis(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), and 3,5-di-tert-butyl-4-hydroxytoluene.

[0139] Examples of the hydroxyphenol include hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-dibutylhydroquinone, 2,5-di-tert-amylhydroquinone, 2-tert-butylmethoxyhydroquinone, 2,3,5-trimethylhydroquinone, 2,5-dichlorohydroquinone, 1,2-dihydroxybenzene, 2-acetylhydroquinone, 4-methylcatechol, 4-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, and 2,3-dihydroxyacetophenone.

[0140] Examples of the aminophenol include o-aminophenol, m-aminophenol, p-aminophenol, 2-(N,N-dimethylamino)phenol, and 4-(ethylamino)phenol.

[0141] Examples of the nitrophenol include o-nitrophenol, m-nitrophenol, p-nitrophenol, and 2,4-dinitrophenol.

[0142] Examples of the nitrosophenol include o-nitrosophenol, m-nitrosophenol, p-nitrosophenol, and α-nitroso-β-naphthol.

[0143] Examples of the alkoxyphenol include 2-methoxyphenol, 2-ethoxyphenol, 2-isopropoxyphenol, 2-tert-butoxyphenol, 4-methoxyphenol, 4-ethoxyphenol, 4-propoxyphenol, 4-butoxyphenol, 4-tert-butoxyphenol, 4-heptyloxyphenol, hydroquinone monobenzyl ether, tert-butyl-4-methoxyphenol, di-tert-butyl-4-methoxyphenol, pyrogallol-1,2-dimethyl ether, and hydroquinone monobenzoate.

[0144] Examples of the tocopherol include α-tocopherol and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran.

[0145] Examples of the quinone-based compound include p-benzoquinone, chloro-p-benzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone, tetrachloro-p-benzoquinone, tetrabromo-p-benzoquinone, 2,3-dimethyl-p-benzoquinone, 2,5-dimethyl-p-benzoquinone, methoxy-p-benzoquinone, and methyl-p-benzoquinone.

[0146] Examples of the nitrobenzene-based compound include nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrobenzene, dinitrodurene, and 2,2-diphenyl-1-picrylhydrazyl.

[0147] Examples of the nitroxide radical compound include 4-hydroxy-2,2,6,6-tetramethyl-piperidin-N-oxyl radical, 4-oxo-2,2,6,6-tetramethyl-piperidin-N-oxyl radical, 4-acetoxy-2,2,6,6-tetramethyl-piperidin-N-oxyl radical, 2,2,6,6-tetramethyl-piperidin-N-oxyl radical, piperidine-1-oxyl radical, 4-(dimethylamino)-2,2,6,6-tetramethyl-piperidin-N-oxyl radical, 4-amino-2,2,6,6-tetramethyl-piperidin-N-oxyl radical, 4-vinyloxy-2,2,6,6-tetramethyl-piperidin-N-oxyl radical, 4-benzoyloxy-2,2,6,6-tetramethyl-piperidin-N-oxyl radical, and 4-(dimethylamino)-2,2,6,6-tetramethyl-piperidin-N-oxyl radical. Oxygen free radical, 2,2,5,5-tetramethyl-piperidin-N-oxyl free radical, 3-amino-2,2,5,5-tetramethyl-piperidin-N-oxyl free radical, 4,4',4"-tris(2,2,6,6-tetramethyl-piperidin-N-oxyl free radical)phosphite, 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl free radical, pyrrolidine-1-oxyl free radical, 2,2,5,5-tetramethyl-1-oxa-3-azacyclopentyl-3-oxyl free radical, 2,2,5,5-tetramethyl-3-pyrroline-1-oxyl free radical-3-carboxylic acid, 2,2,3,3,5,5,6,6-octamethyl-1,4-diazacyclohexyl-1,4-dioxyl free radical, di-tert-butylnitroxide, di-tert-amylnitroxide.

[0148] Examples of the amine compound include N,N-diphenylamine, alkylated diphenylamine, 4,4'-dicumyl diphenylamine, 4,4'-dioctyl diphenylamine, 4-amino diphenylamine, p-nitroso diphenylamine, N-nitrosodinaphthylamine, N-nitroso diphenylamine, N-nitrosophenylnaphthylamine, N-nitrosophenylhydroxylamine, N,N'-dialkyl p-phenylenediamine (the alkyl groups may be the same or different and each independently have 1 to 4 carbon atoms and may be linear or branched), N,N'-diphenyl p-phenylenediamine, N-phenyl-N'-isopropyl p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, N, N'-di(2-naphthyl)-p-phenylenediamine, N,N-diethylhydroxylamine, 1,4-phenylenediamine, N-(1,4-dimethylpentyl)-N'-phenyl-1,4-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, butyral-α-naphthylamine, N-phenyl-β-naphthylamine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

[0149] Examples of the phosphorus-containing compound include triphenylphosphine, triphenyl phosphite, triethyl phosphite, tris(isodecyl) phosphite, tris(tridecyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, [1,1-diphenyl-4,4'-diyl-bis[tetrakis-2,4-bis(1,1-dimethylethyl)phenyl]]phosphonate, triphenyl phosphite, tris(nonylphenyl) phosphite, 4,4'-isopropylidene diphenol alkyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and terphenyl phosphite. esters, distearyl pentaerythritol diphosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetra(tridecyl)-4,4'-butylidene bis(3-methyl-6-tert-butylphenol) diphosphite, hexa(tridecyl)-1,1,3-tri(2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester, bis(4-tert-butylphenyl) phosphate sodium salt, 2,2'-methylene-bis(4,6-di-tert-butylphenyl) phosphate sodium salt, 1,3-bis(diphenoxyphosphoryloxy)benzene.

[0150] Examples of the sulfur-containing compound include diphenyl sulfide, phenothiazine, 3-oxophenothiazine, 5-oxophenothiazine, phenothiazine dimer, 1,4-dimercaptobenzene, 1,2-dimercaptobenzene, 2-mercaptophenol, 4-mercaptophenol, 2-(methylthio)phenol, and 3,7-bis(dimethylamino)phenothiazine. Chloride, sulfur (elemental).

[0151] As the iron-containing compound, for example, iron (III) chloride can be exemplified.

[0152] Examples of the copper-containing compound include copper dimethyldithiocarbamate, copper diethylthiocarbamate, copper dibutylthiocarbamate, copper salicylate, copper acetate, copper thiocyanate, copper nitrate, copper chloride, copper carbonate, copper hydroxide, copper acrylate, and copper methacrylate.

[0153] Examples of the manganese-containing compound include manganese dialkyldithiocarbamate (the alkyl group is any of methyl, ethyl, propyl, and butyl, and may be the same or different), manganese diphenyldithiocarbamate, manganese formate, manganese acetate, manganese octoate, manganese naphthenate, manganese permanganate, and manganese salts of ethylenediaminetetraacetic acid.

[0154] As the polymerization inhibitor, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, N,N′-dialkyl-p-phenylenediamine, phenothiazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl radical are preferred because the effect of improving storage stability is easily exhibited.

[0155] The ester compound-containing composition of the embodiment may contain other components besides the ester compound (1), component A and component B.

[0156] Examples of other components include release agents, lubricants, plasticizers, antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, polymerization inhibitors, fillers, pigments, dyes, silane coupling agents, leveling agents, defoaming agents, fluorescent agents and other additives.

[0157] The ester compound-containing composition of the embodiment may contain unreacted raw materials during production of the ester compound-containing composition, such as methyl (meth)acrylate, alcohol, and (meth)acrylic acid.

[0158] The composition containing an ester compound according to one example of the embodiment may contain a (meth)acrylate other than the ester compound (1).

[0159] (composition)

[0160] The content of the ester compound (1) in the composition containing the ester compound is preferably 85.00% by mass or more, more preferably 90.00% by mass or more, and further preferably 95.00% by mass or more, relative to the total mass of the composition containing the ester compound. In addition, the content of the ester compound (1) is preferably 99.99% by mass or less, more preferably 99.97% by mass or less, and further preferably 99.95% by mass or less, relative to the total mass of the composition containing the ester compound.

[0161] The lower limit and upper limit of the preferred content of the ester compound (1) may be arbitrarily combined, and for example, it is preferably 85.00 to 99.99% by mass, more preferably 90.00 to 99.97% by mass, and further preferably 95.00 to 99.95% by mass.

[0162] The content of component A in the composition containing an ester compound is 1 to 1500 ppm by mass relative to the total mass of the composition containing an ester compound. When the content of component A is within the above range, the dimerization of the ester compound (1) and the reduction in purity of the ester compound (1) due to the generation of oxidation products can be suppressed.

[0163] Since the dimerization of the ester compound (1) and the generation of oxidation products can be easily inhibited, the content of component A is preferably 1 ppm by mass or more, and more preferably 3 ppm by mass or more. Since the amount of impurities during the production of the (meth)acrylic acid polymer is reduced and the deterioration of the physical properties of the (meth)acrylic acid polymer can be easily inhibited, the content of component A is preferably 1500 ppm by mass or less, and more preferably 1200 ppm by mass or less.

[0164] The lower limit and upper limit of the preferred content of Component A may be arbitrarily combined, and for example, it is preferably 1 to 1500 mass ppm, and more preferably 3 to 1200 mass ppm.

[0165] The content of component B in the composition containing the ester compound is preferably 1 mass ppm or more, more preferably 3 mass ppm or more, and further preferably 5 mass ppm or more, relative to the total mass of the composition containing the ester compound. If the content of component B is above the above lower limit, it is easy to obtain the effect of suppressing the dimerization of the ester compound (1) and the generation of oxidation products. The content of component B is preferably 1500 mass ppm or less, more preferably 1200 mass ppm or less, and further preferably 1000 mass ppm or less, relative to the total mass of the composition containing the ester compound. If the content of component B is below the above upper limit, the amount of impurities when manufacturing the (meth)acrylic acid polymer is reduced, and it is easy to suppress the reduction of the physical properties of the (meth)acrylic acid polymer.

[0166] The lower limit and upper limit of the preferred content of Component B may be arbitrarily combined, and for example, it is preferably 1 to 1500 mass ppm, more preferably 3 to 1200 mass ppm, and further preferably 5 to 1000 mass ppm.

[0167] The water content of the composition containing the ester compound needs to be 5000 mass ppm or less because it adversely affects the physical properties of the (meth)acrylic polymer.

[0168] The water content of the composition containing the ester compound is preferably 5000 mass ppm or less, more preferably 4000 mass ppm or less, and further preferably 3000 mass ppm or less.

[0169] (Analysis of Composition Containing Ester Compound)

[0170] Component A and component B contained in the composition containing an ester compound can be measured by, for example, GC-MS measurement.

[0171] In the GC-MS spectrum of the composition containing an ester compound, if there is a peak at the same retention time as the standard of component A, and the m / z value detected in the mass spectrum of the peak is consistent with the exact mass of component A, it can be determined that the composition containing an ester compound contains component A. In the case where a standard of component A cannot be obtained, when the pattern of the mass spectrum of the peak appearing in the GC-MS spectrum of the composition containing an ester compound is consistent with the pattern of the mass spectrum of component A included in the mass spectrum database, it can be determined that the peak is the peak of component A and the composition containing an ester compound contains component A. As examples of mass spectrum databases, NIST20, NIST17, NIST14, NIST14s, etc. can be exemplified. In addition, when the volatility is low and cannot be detected by GC-MS measurement, LC-MS can be used for detection. Component B can also be confirmed by the same method as component A.

[0172] The content of the ester compound (1) can be calculated by performing GC-FID measurement on a composition containing the ester compound, determining the amount by using an area percentage method, and correcting the amount of water determined by a Karl Fischer titrator.

[0173] The content of component A can be determined by, for example, GC measurement of a composition containing an ester compound and using an internal standard method. If a standard substance of component A is not available and cannot be determined by the internal standard method, the content of component A can be calculated by GC-FID measurement of any organic compound whose content is known using the following formula.

[0174]

[0175] In the above formula, N is the number of carbon atoms contained in one molecule of any organic compound. A is the number of carbon atoms contained in one molecule of component A, S A is the peak area of ​​component A, S is the peak area of ​​any organic compound, and M is the content (mass ppm) of any organic component.

[0176] When volatility is low and quantification by GC area is not possible, quantification by chromatography such as LC can be used.

[0177] The content of component B can also be calculated by the same method as that of component A.

[0178] The water content of the composition containing the ester compound can be confirmed by the Karl Fischer method.

[0179] [Method for producing a composition containing an ester compound]

[0180] The composition containing an ester compound of the present invention can be produced by, for example, performing an ester exchange reaction between methyl (meth)acrylate and an alcohol (a) having 2 to 20 carbon atoms in the presence of Component A.

[0181] As the alcohol (a), it is preferred to use at least one selected from the following alcohols (a1) to (a3).

[0182] (a1) Monohydric alcohol having 2 to 20 carbon atoms

[0183] (a2) at least one alcohol selected from diols having 2 to 8 carbon atoms and triols having 2 to 8 carbon atoms

[0184] (a3) Alcohols having 2 to 8 carbon atoms and containing an ether bond

[0185] Methyl (meth)acrylate is particularly prone to dimerization among (meth)acrylates and to the formation of methyl pyruvate due to oxidation. However, by carrying out the transesterification reaction in the presence of component A, dimerization of methyl (meth)acrylate and the formation of methyl pyruvate are suppressed, and as a result, the yield of the ester compound (1) is improved.

[0186] By carrying out an ester exchange reaction between methyl (meth)acrylate and the alcohol (a1) in the presence of Component A, an ester compound-containing composition containing the ester compound (1-1) can be produced.

[0187] More specifically, for example, in a reactor, in the presence of a catalyst and component A, methyl (meth)acrylate and alcohol (a1) are transesterified as shown in the following formula (2). a1 and R a2 With R in formula (1-1) a1 and Ra2 same.

[0188]

[0189] Examples of the alcohol (a1) include ethanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, isobornyl alcohol, allyl alcohol, phenol, and benzyl alcohol. The alcohol (a1) may be used alone or in combination of two or more.

[0190] The alcohol (a1) preferably includes a linear or branched monohydric alcohol having 2 to 20 carbon atoms.

[0191] The ratio of the charging amount of methyl (meth)acrylate to the alcohol (a1) can be appropriately determined. From the viewpoint of improving productivity, the ratio of methyl (meth)acrylate to 1 mol of the alcohol (a1) is preferably 0.1 mol to 10 mol, more preferably 0.3 mol to 4 mol.

[0192] By carrying out an ester exchange reaction between methyl (meth)acrylate and the alcohol (a2) in the presence of Component A, an ester compound-containing composition containing the ester compound (1-2) can be produced.

[0193] More specifically, for example, in a reactor, in the presence of a catalyst and component A, methyl (meth)acrylate and alcohol (a2) are transesterified as represented by the following formula (3) and the following formula (4).

[0194] Among them, R in formula (3) and formula (4) b1 ~R b3 , R b5 ~R b7 and R in formulas (1-21) to (1-23) b1 ~R b3 , R b5 ~R b7 In addition, R b41 is a linear or branched alkylene group having 2 to 8 carbon atoms, R b42 It is a linear or branched hydroxyalkylene group having 2 to 8 carbon atoms.

[0195]

[0196] Examples of the alcohol (a2) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, and trimethylolpropane. Among them, the alcohol (a2) preferably contains at least one selected from ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and trimethylolpropane.

[0197] As the alcohol (a2), one type may be used alone, or two or more types may be used in combination.

[0198] The ratio of the charging amount of methyl (meth)acrylate to the alcohol (a2) can be appropriately determined. From the viewpoint of improving productivity, the ratio of methyl (meth)acrylate to 1 mol of the alcohol (a2) is preferably 0.1 mol to 10 mol, more preferably 0.3 mol to 4 mol.

[0199] By carrying out an ester exchange reaction between methyl (meth)acrylate and the alcohol (a3) ​​in the presence of Component A, an ester compound-containing composition containing the ester compound (1-3) can be produced.

[0200] More specifically, for example, in a reactor, in the presence of Ti(OR)4 (R is an alkyl group) and component A as a catalyst, methyl (meth)acrylate and alcohol (a3) ​​are transesterified as shown in the following formula (5). c1 and R c2 and R in formula (1-3) c1 and R c2 same.

[0201]

[0202] The number of ether bonds possessed by the alcohol (a3) ​​is preferably one, but is not limited.

[0203] Examples of the alcohol (a3) ​​include 2-methoxyethanol, glycidyl alcohol, and tetrahydrofurfuryl alcohol. The alcohol (a3) ​​may be used alone or in combination of two or more.

[0204] The alcohol (a3) ​​preferably contains one selected from the group consisting of 2-methoxyethanol, glycidyl alcohol, and tetrahydrofurfuryl alcohol.

[0205] The ratio of the charging amount of methyl (meth)acrylate to the alcohol (a3) ​​can be appropriately determined. From the viewpoint of improving productivity, the ratio of methyl (meth)acrylate to 1 mol of the alcohol (a3) ​​is preferably 0.1 mol to 10 mol, more preferably 0.3 mol to 4 mol.

[0206] By carrying out an ester exchange reaction between methyl (meth)acrylate and two or more selected from alcohols (a1) to (a3) ​​in the presence of Component A, a composition containing two or more of the ester compounds (1-1) to (1-3) can be produced.

[0207] At this time, the ratio of the charging amount of methyl (meth)acrylate to the alcohol (a) can be appropriately determined. From the viewpoint of improving productivity, the ratio of methyl (meth)acrylate to 1 mol of the alcohol (a) is preferably 0.1 mol to 10 mol, more preferably 0.3 mol to 4 mol.

[0208] The reactor is preferably a reactor equipped with a distillation column. Since the transesterification reaction is an equilibrium reaction, the productivity can be improved by separating the by-product methanol using a distillation column. For example, it is preferred to carry out the transesterification reaction while separating methanol from the system in the form of an azeotropic mixture with methyl (meth)acrylate.

[0209] Examples of such a reactor include a reactor equipped with a distillation tower on the top of a reaction vessel called a reactor, and a distillation tower in which a distillation pot can be used as a reaction vessel. Examples of the distillation tower include a packed tower type and a tray type distillation tower.

[0210] The number of theoretical plates of the distillation column is preferably 5 or more, more preferably 7 or more, from the viewpoint of high separation capability and stable operation.

[0211] There is no particular limitation on the catalyst used, and examples thereof include hydroxides, carbonates, and bicarbonates of alkali metals such as lithium, sodium, and potassium; oxides, hydroxides, and carbonates of alkaline earth metals such as magnesium and calcium; alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, and potassium tert-butoxide; alkali metal amides such as lithium amide, sodium amide, and potassium amide; titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetra(2-ethylhexyl) titanate; and tin compounds such as dibutyltin oxide and dioctyltin oxide. Among them, titanium alkoxides, dibutyltin oxide, and dioctyltin oxide are preferred because of the small amount of by-products of the Michael addition reaction in the transesterification reaction and the high catalyst activity. The catalyst may be used alone or in combination of two or more.

[0212] The catalyst may be supplied to the reactor alone, or dissolved in the same alcohol as the raw material alcohol (a), or dissolved in the raw material (meth)acrylate. For example, there may be exemplified a method in which a catalyst dissolved in all of the alcohol (a) used in the reaction is supplied to the reactor, or a method in which a catalyst dissolved in a portion of the alcohol (a) used in the reaction is supplied to the reactor.

[0213] The amount of the catalyst used is preferably 0.001 mol% to 1 mol%, more preferably 0.01 mol% to 0.1 mol%, based on 1 mol of the alcohol (a).

[0214] A solvent may be used in the transesterification reaction. When a solvent is used, it is preferred to use a solvent that forms an azeotropic composition with methanol produced as a by-product.

[0215] Examples of the solvent include n-pentane, n-hexane, n-heptane, n-octane, 2,3-dimethylbutane, 2,5-dimethylhexane, 2,2,4-trimethylpentane, cyclohexane, benzene, and toluene. Among them, n-hexane, n-heptane, and cyclohexane are preferred. As the solvent, one may be used alone, or two or more may be used in combination.

[0216] The reaction temperature of the transesterification reaction also varies depending on the types of the alcohol (a) and the solvent, but is preferably 60°C to 150°C.

[0217] The reaction pressure of the transesterification reaction is not particularly limited, and the reaction may be carried out under any pressure of reduced pressure, normal pressure, or increased pressure.

[0218] The form of the transesterification reaction is not particularly limited, and for example, it can be carried out by a generally used method such as a batch reaction or a continuous reaction.

[0219] After the transesterification reaction, the reaction solution may be purified to separate unreacted raw materials and by-products. Purification may be carried out by various methods such as distillation, crystallization, extraction, column chromatography, etc.

[0220] The reaction solution may be mixed with component B to carry out the transesterification reaction. The presence of component B in addition to component A further suppresses dimerization of methyl (meth)acrylate and production of methyl pyruvate, thereby more easily achieving the effect of improving the yield of the ester compound (1).

[0221] Component B may be added to the solution containing the ester compound (1) and component A after the transesterification reaction. In this case, a solution containing the ester compound (1) and component B (liquid B) different from the solution containing the ester compound (1) and component A (liquid A) may be prepared, and the liquid A and liquid B may be mixed to prepare a composition containing an ester compound. Alternatively, the ester compound (1), liquid A, and liquid B may be mixed to prepare a composition containing an ester compound.

[0222] The method for producing the ester compound-containing composition of the present invention is not limited to the above method.

[0223] For example, other (meth)acrylates other than methyl (meth)acrylate may be used instead of methyl (meth)acrylate as a raw material.

[0224] The ester compound (1) can also be produced by an esterification reaction of the alcohol (a) and (meth)acrylic acid.

[0225] (Polymerizable composition)

[0226] The polymerizable composition of the present invention is a polymerizable composition for producing a (meth)acrylic polymer, and includes the composition containing the ester compound of the present invention.

[0227] In one embodiment, a composition containing an ester compound that has been stored for one day or more after production can be used in a polymerizable composition.

[0228] The storage time of the composition containing the ester compound may be 1 day or more, 3 days or more, 7 days or more, or 14 days or more. In addition, the storage time of the composition containing the ester compound may be 180 days or less, 150 days or less, 120 days or less, or 90 days or less. It should be noted that the "storage time" is not limited to the time left to stand under a specific environment, but refers to the time elapsed from the time of production including the time of transportation, etc.

[0229] The material of the storage container for the composition containing an ester compound is not particularly limited, and for example, a metal container such as stainless steel, a resin container, or a glass container can be used. Either a transparent container or an opaque container can be used.

[0230] The temperature when storing the composition containing the ester compound is preferably -10°C or higher, more preferably 0°C or higher, and preferably 60°C or lower, more preferably 50°C or lower. By keeping the temperature at -10°C or higher, the load on the cooling device can be reduced, and by keeping the temperature at 60°C or lower, the generation of dimers and oxidation products of the (meth)acrylate can be easily suppressed.

[0231] The oxygen concentration in the gas phase when the composition containing the ester compound is stored is preferably 5% by volume or more, more preferably 7% by volume or more, and preferably 30% by volume or less, more preferably 22% by volume or less. By setting the oxygen concentration in the gas phase to 5% by volume or more, it is easy to prevent the inadvertent polymerization of the ester compound by utilizing the polymerization prevention effect of oxygen, and by setting the oxygen concentration in the gas phase to 30% by volume or less, it is easy to suppress the oxidation of (meth)acrylate by oxygen to generate various impurities.

[0232] In the embodiment, the stored ester compound-containing composition may be used as a polymerizable composition without further adding a monomer, or may be made into a polymerizable composition by further adding another monomer copolymerizable with the ester compound (1).

[0233] In one embodiment, the produced ester compound-containing composition may be stored in a state where other monomers copolymerizable with the ester compound (1) are added and then used as a polymerizable composition. In this case, it is preferred that no polymerization initiator is added during storage.

[0234] The ratio of the ester compound (1) to the total mass of the monomers in the polymerizable composition is preferably 10 mass % or more, more preferably 20 mass % or more, and is preferably 90 mass % or less, more preferably 80 mass % or less.

[0235] Examples of other monomers copolymerizable with the ester compound (1) include methyl (meth)acrylate, unsaturated carboxylic acids, unsaturated carboxylic anhydrides, maleimide, hydroxyl-containing vinyl monomers, vinyl esters, nitrogen-containing vinyl monomers, epoxy-containing monomers, aromatic vinyl monomers, alkanediol di(meth)acrylates, polyoxyalkylene glycol di(meth)acrylates, and vinyl monomers having two or more ethylenically unsaturated bonds in the molecule.

[0236] Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, and itaconic acid.

[0237] Examples of the unsaturated carboxylic anhydride include maleic anhydride and itaconic anhydride.

[0238] Examples of maleimide include N-phenylmaleimide and N-cyclohexylmaleimide.

[0239] Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate.

[0240] Examples of the vinyl ester include vinyl acetate and vinyl benzoate.

[0241] Examples of the nitrogen-containing vinyl monomer include methacrylamide and acrylonitrile.

[0242] Examples of the epoxy group-containing monomer include glycidyl acrylate and glycidyl methacrylate.

[0243] Examples of the aromatic vinyl monomer include styrene and α-methylstyrene.

[0244] Examples of the alkanediol di(meth)acrylate include ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

[0245] Examples of the polyoxyalkylene glycol di(meth)acrylate include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0246] Examples of the vinyl monomer having two or more ethylenically unsaturated bonds in the molecule include divinylbenzene.

[0247] As other monomers, vinyl chloride, vinylidene chloride and derivatives thereof, unsaturated polyester prepolymers obtained from at least one polycarboxylic acid including an ethylenically unsaturated polycarboxylic acid and at least one diol, and vinyl ester prepolymers obtained by acrylic acid-modifying the ends of epoxy groups may be used.

[0248] The other monomers may be used alone or in combination of two or more.

[0249] The polymerizable composition of the embodiment preferably further contains a polymerization initiator.

[0250] Examples of the polymerization initiator include azo compounds, organic peroxides, persulfate compounds, and redox polymerization initiators. The polymerization initiator may be used alone or in combination of two or more.

[0251] Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 1,1-azobis(cyclohexanecarbonitrile), and dimethyl 2,2'-azobisisobutyrate.

[0252] Examples of the organic peroxide include benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyacetate, tert-hexyl peroxyisopropyl monocarbonate, and tert-butyl peroxyacetate. Ester, tert-hexyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxyethylhexanoate, 1,1,2-trimethylpropyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxyisopropyl monocarbonate, 1,1,2-trimethylpropyl peroxyisopropyl monocarbonate, 1,1,3,3-tetramethylbutyl peroxyisononanoate, 1,1,2-trimethylpropyl peroxyisononanoate, di-tert-butyl peroxide, di-tert-hexyl peroxide, lauroyl peroxide, dilauroyl peroxide.

[0253] As the persulfate compound, potassium persulfate can be exemplified.

[0254] The amount of the polymerization initiator added is not particularly limited, and may be, for example, 0.005 to 5 parts by mass based on 100 parts by mass of the total mass of the monomers in the polymerizable composition.

[0255] The content of at least one compound selected from transition metal compounds and compounds of Group IIIA elements in the polymerizable composition of the embodiment, component C, is preferably 7×10 4 Thereby, the weather resistance of the obtained (meth)acrylic polymer becomes good and yellowing is suppressed.

[0256] The reason is considered to be as follows.

[0257] Compared with the ester compound (1) as a conjugated monomer, the α-olefin as component A cannot obtain the resonance stabilization effect and has significantly lower reactivity. Therefore, unless a specific polymerization catalyst such as component C is used and the special conditions that the effect as a catalyst is not exerted, unreacted α-olefin remains in the obtained (meth)acrylic polymer. It is believed that the (meth)acrylic polymer having unreacted α-olefin remaining has good weather resistance and suppressed yellowing.

[0258] The content of component C is preferably 7×10 4 mass ppm or less, more preferably 1×10 4 The content of the component C is preferably 1000 ppm by mass or less, more preferably 1000 ppm by mass or less, and particularly preferably contains no component C. Here, "containing no component C" means that the content is less than the detection limit in GC-MS measurement.

[0259] Examples of component C include compounds of transition metals of Group VB to Group IIB having a chelating ligand and Lewis acid catalysts.

[0260] Specific examples of transition metals include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, platinum, ruthenium, cobalt, rhodium, nickel, palladium, and copper. Among them, as transition metals, transition metals of Groups VIII to IB are preferred, transition metals of Group VIII are more preferred, and nickel or palladium is further preferred. These transition metals may be used alone or in combination of two or more.

[0261] The chelating ligand has at least two atoms selected from P, N, O and S, including ligands as bidentate or multidentate ligands, and is electron neutral or anionic. The structure of the chelating ligand is exemplified in the review by Ittel et al. (Ittel et al., "Late-Metal Catalysts for Ethylene Homo-and Copolymerization", Chemical Reviews, March 25, 2000, Vol. 100, No. 4, p. 1169-1204).

[0262] As chelating ligands, for example, bidentate anionic P, O ligands can be exemplified. As the above-mentioned bidentate anionic P, O ligands, for example, phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol and phosphorus enol compounds can be exemplified. As chelating ligands other than the above-mentioned bidentate anionic P, O ligands, for example, bidentate anionic N, O ligands can be exemplified. As the above-mentioned bidentate anionic N, O ligands, for example, salicylaldehyde imine salts and pyridine carboxylic acid can be exemplified. As chelating ligands other than the above-mentioned bidentate anionic P, O ligands and the above-mentioned bidentate anionic N, O ligands, for example, diimine ligands, diphenyl oxide ligands and diamide ligands can be exemplified.

[0263] As catalysts of compounds of transition metals of Groups VB to IB as representative chelating ligands, there are known catalysts such as SHOP catalysts and Drent catalysts. SHOP catalysts are catalysts in which a phosphorus-based ligand having an aromatic group which may have a substituent is coordinated to a nickel metal. In addition, Drent catalysts are catalysts in which a phosphorus-based ligand having an aromatic group which may have a substituent is coordinated to a palladium metal.

[0264] In addition, as a representative Lewis acid catalyst, a cationic complex of divalent palladium or platinum can be exemplified. The cationic complex of divalent palladium or platinum shows Lewis acidity and is useful as a Lewis acid catalyst for Diels-Alder reaction, etc. In addition, compounds of boron and aluminum of Group IIIA elements, titanium of the fourth period transition metal, and zirconium of the fifth period transition metal also show Lewis acidity and are therefore preferred.

[0265] In one example of an embodiment, various additives such as a release agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid, an inhibitor, a filler, a pigment, a dye, a silane coupling agent, a leveling agent, a defoaming agent, a fluorescent agent, and a chain transfer agent can be added to the composition containing the ester compound after storage as needed.

[0266] [Method for producing (meth)acrylic acid polymer]

[0267] The (meth)acrylic polymer can be produced by polymerizing the polymerizable composition of the present invention.

[0268] The polymerization method is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. Bulk polymerization is preferred from the viewpoint of environmental load caused by the use of solvents and the transparency of the obtained (meth)acrylic polymer.

[0269] The specific method of the bulk polymerization method is not particularly limited, and examples thereof include known injection molding polymerization methods such as a unit casting method and a continuous casting method.

[0270] The polymerization temperature is preferably 125°C to 210°C, more preferably 130°C to 180°C.

[0271] The polymerization time is preferably 0.5 to 24 hours.

[0272] The weight average molecular weight (Mw) of the (meth)acrylic acid-based polymer is not particularly limited, and may be, for example, 100000 to 1000000. The larger the Mw of the (meth)acrylic acid-based polymer, the more solvent resistance and chemical resistance can be improved.

[0273] The Mw of the (meth)acrylic polymer can be controlled by adjusting the polymerization temperature, the polymerization time, the amount of the polymerization initiator added, and the like.

[0274] (composition)

[0275] The content of the ester compound (I) in the composition containing the ester compound is preferably 85.00% by mass or more, more preferably 90.00% by mass or more, and further preferably 95.00% by mass or more, relative to the total mass of the composition containing the ester compound. In addition, the content of the ester compound (I) is preferably 99.99% by mass or less, more preferably 99.97% by mass or less, and further preferably 99.95% by mass or less, relative to the total mass of the composition containing the ester compound.

[0276] The lower limit and upper limit of the preferred content of the ester compound (I) may be arbitrarily combined, and for example, it is preferably 85.00 to 99.99% by mass, more preferably 90.00 to 97.97% by mass, and further preferably 95.00 to 99.95% by mass.

[0277] The ratio of the ester compound (I) to the total mass of the monomers in the polymerizable composition is preferably 10 mass % or more, more preferably 20 mass % or more, and is preferably 90 mass % or less, more preferably 80 mass % or less.

[0278] Examples of other monomers copolymerizable with the ester compound (I) include methyl (meth)acrylate, unsaturated carboxylic acids, unsaturated carboxylic anhydrides, maleimides, vinyl esters, nitrogen-containing vinyl monomers, epoxy-containing monomers, aromatic vinyl monomers, polyoxyalkylene glycol di(meth)acrylates, and vinyl monomers having two or more ethylenically unsaturated bonds in the molecule.

[0279] Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to the following description.

[0280] <Ester compound-containing composition containing ester compound (1-1)>

[0281] [GC-MS measurement]

[0282] The analysis of the composition containing an ester compound after storage was performed using GC-MS, and the composition was determined by the method described in the above section "Analysis of the composition containing an ester compound." The GC-MS measurement was performed using QP-2010 Ultra manufactured by Shimadzu Corporation.

[0283] (GC conditions)

[0284] Column (Product name: InertCap1, manufactured by GL Sciences)

[0285] Length: 60m, inner diameter: 0.25mm, film thickness: 1.50μm

[0286] Injection volume: 1.0 μL

[0287] Gasification chamber temperature: 280℃

[0288] Column oven temperature: maintain at 150°C for 1 minute, increase the temperature from 150°C to 260°C at 2.5°C / min, and maintain at 260°C for 15 minutes.

[0289] Carrier gas: Helium

[0290] Injection mode: split (split ratio 25)

[0291] Control mode: Constant linear speed (35.0 cm / s)

[0292] Pressure: 262.8kPa

[0293] Total flow rate: 47.2mL / min

[0294] Purge flow rate: 3.0mL / min

[0295] Column flow rate: 1.70mL / min

[0296] (MS conditions)

[0297] Ionization method: EI (Electron Ionization)

[0298] Ion source temperature: 200°C

[0299] Interface temperature: 300℃

[0300] m / z detection range: 30~600

[0301] Testing time: 60 minutes

[0302] [Water content]

[0303] The moisture content was quantitatively determined by the Karl Fischer method using a trace moisture measuring device (product name: CA-200, manufactured by Nitto Seiko Analytical Science Co., Ltd.).

[0304] [Example A1]

[0305] Liquid A was prepared by adding 0.0208 g of 1-octane as component A to 10.0014 g of butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 164 mass ppm).

[0306] Separately, 0.0200 g of 2,4-dimethyl-6-tert-butylphenol as component B was added to 10.0089 g of BMA (water content: 164 mass ppm) to prepare liquid B.

[0307] Next, 0.0276 g of liquid A and 0.0297 g of liquid B were added to 4.9998 g of BMA (water content: 164 mass ppm) to prepare a composition containing an ester compound.

[0308] The obtained composition containing an ester compound was stored at 25°C for 21 days, and then the amount of BMA dimer generated (mass ppm) was determined from the ratio (area %) of the area value of BMA dimer to the total area value of all components detected by GC-MS. In addition, the BMA purity (%) was calculated from the ratio (area %) of the area value of BMA to the total area value of all components detected. When calculating the BMA dimer and BMA purity, the value obtained by subtracting the water content (mass %) from 100% was multiplied by the area % of each component.

[0309] [Examples A2 to A10, Comparative Example A1]

[0310] A composition containing an ester compound was prepared in the same manner as in Example A1 except that the compositions of liquid A, liquid B, and the composition containing an ester compound were changed as shown in Table 1, and the amount of BMA dimer produced and the BMA purity were determined.

[0311] [Table 1]

[0312]

[0313] The abbreviations in Table 1 have the following meanings.

[0314] BMA: Butyl Methacrylate

[0315] Oct:1-octene

[0316] 2EH: 2-ethyl-1-hexene

[0317] Ddc: 1-dodecene

[0318] DMTBP: 2,4-dimethyl-6-tert-butylphenol

[0319] 4MP: 4-methoxyphenol

[0320] IPPPD: N-isopropyl-N'-phenyl-p-phenylenediamine

[0321] PHT: Phenothiazine

[0322] HO-TEMPO: 4-Hydroxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl radical

[0323] Table 2 shows the results of measuring the amount of BMA dimer produced and the BMA purity in each example.

[0324] [Table 2]

[0325] [Table 2]

[0326]

[0327] As shown in Table 2, the ester compound-containing compositions of Examples A1 to A10 containing Component A showed less BMA dimer generation after storage and higher BMA purity than the ester compound-containing composition of Comparative Example A1 not containing Component A.

[0328] [Examples A11 to A13, Comparative Examples A2 and A3]

[0329] Ethyl methacrylate (EMA, manufactured by Tokyo Chemical Industry, water content 245 mass ppm) was used instead of BMA, and the compositions of liquid A, liquid B, and the composition containing the ester compound were changed as shown in Table 3. The composition containing the ester compound was prepared in the same manner as in Example A1, and the EMA purity was determined. The results are shown in Table 4.

[0330] [Table 3]

[0331]

[0332] [Table 4]

[0333] [Table 4]

[0334]

[0335] As shown in Table 4, the ester compound-containing compositions of Examples A11 to A13 containing Component A had higher EMA purity after storage than the ester compound-containing compositions of Comparative Examples A2 and A3 not containing Component A.

[0336] <Ester compound-containing composition containing ester compound (1-2)>

[0337] [GC-MS measurement]

[0338] The analysis of the composition containing an ester compound after storage was performed using GC-MS, and the composition was determined by the method described in the above section "Analysis of the composition containing an ester compound." The GC-MS measurement was performed using QP-2010 Ultra manufactured by Shimadzu Corporation.

[0339] (GC conditions)

[0340] Column (Product name: InertCap1, manufactured by GL Sciences)

[0341] Length: 60m, inner diameter: 0.25mm, film thickness: 1.50μm

[0342] Injection volume: 1.0 μL

[0343] Gasification chamber temperature: 280℃

[0344] Column oven temperature: When analyzing a composition containing 2-hydroxymethyl acrylate, keep it at 150°C for 1 minute, increase the temperature from 150°C to 260°C at 2.5°C / min, and keep it at 260°C for 15 minutes. When analyzing a composition containing ethylene glycol dimethacrylate, keep it at 200°C for 1 minute, increase the temperature from 200°C to 260°C at 2.0°C / min, and keep it at 260°C for 29 minutes.

[0345] Carrier gas: Helium

[0346] Injection mode: split (split ratio 25)

[0347] Control mode: Constant linear speed (35.0 cm / s)

[0348] Pressure: 262.8kPa

[0349] Total flow rate: 47.2mL / min

[0350] Purge flow rate: 3.0mL / min

[0351] Column flow rate: 1.70mL / min

[0352] (MS conditions)

[0353] Ionization method: EI (Electron Ionization)

[0354] Ion source temperature: 200°C

[0355] Interface temperature: 300℃

[0356] m / z detection range: 30~600

[0357] Testing time: 60 minutes

[0358] [Water content]

[0359] The moisture content was quantitatively determined by the Karl Fischer method using a trace moisture measuring device (product name: CA-200, manufactured by Nitto Seiko Analytical Science Co., Ltd.).

[0360] [Example B1]

[0361] Liquid A was prepared by adding 0.0224 g of 2-ethyl-1-hexene as component A to 10.0028 g of 2-hydroxyethyl methacrylate (HEMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 247 mass ppm).

[0362] Separately, 0.0218 g of 2,4-dimethyl-6-tert-butylphenol as component B was added to 10.0158 g of HEMA (water content: 247 mass ppm) to prepare liquid B.

[0363] Next, 0.0304 g of liquid A and 0.0334 g of liquid B were added to 5.0098 g of HEMA (water content: 247 mass ppm) to prepare a composition containing an ester compound.

[0364] After the obtained composition containing an ester compound was stored at 25°C for 21 days, the HEMA purity (%) was calculated from the ratio (area %) of the area value of HEMA to the total area values ​​of all components detected by GC-MS measurement. In the calculation, the value obtained by subtracting the water content (mass %) from 100% was multiplied by the area % of HEMA.

[0365] [Examples B2 to B5, Comparative Examples B1 to B3]

[0366] Except that the compositions of liquid A, liquid B, and the composition containing an ester compound were changed as shown in Table 5, a composition containing an ester compound was prepared in the same manner as in Example B1, and the HEMA purity was determined.

[0367] [Table 5]

[0368]

[0369] The abbreviations in Table 5 have the following meanings. HEMA: 2-hydroxyethyl methacrylate

[0370] Oct:1-octene

[0371] 2EH: 2-ethyl-1-hexene

[0372] DMTBP: 2,4-dimethyl-6-tert-butylphenol

[0373] 4MP: 4-methoxyphenol

[0374] IPPPD: N-isopropyl-N'-phenyl-p-phenylenediamine

[0375] HO-TEMPO: 4-Hydroxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl radical

[0376] Table 6 shows the results of measuring the HEMA purity in each example.

[0377] [Table 6]

[0378] [Table 6]

[0379]

[0380] As shown in Table 6, the ester compound-containing compositions of Examples B1 to B5 containing Component A also had higher HEMA purity after storage than the ester compound-containing compositions of Comparative Examples B1 to B3 not containing Component A.

[0381] [Examples B6 to B7, Comparative Examples B4 to B6]

[0382] Ethylene glycol dimethacrylate (EDMA, water content 91 mass ppm) was used instead of HEMA, and the compositions of liquid A, liquid B, and the composition containing the ester compound were changed as shown in Table 7. The composition containing the ester compound was prepared in the same manner as in Example B1, and the purity of EDMA was determined. The results are shown in Table 8.

[0383] [Table 7]

[0384]

[0385] [Table 8]

[0386] [Table 8]

[0387]

[0388] As shown in Table 8, the ester compound-containing compositions of Examples B3 to B4 containing Component A had higher EDMA purity after storage than the ester compound-containing compositions of Comparative Examples B4 to B5 not containing Component A and Comparative Example B6 containing a large amount of Component A.

[0389] <Ester compound-containing composition containing ester compound (1-3)>

[0390] [GC-MS measurement]

[0391] The analysis of the composition containing an ester compound after storage was performed using GC-MS, and the composition was determined by the method described in the above section "Analysis of the composition containing an ester compound." The GC-MS measurement was performed using QP-2010 Ultra manufactured by Shimadzu Corporation.

[0392] (GC conditions)

[0393] Column (Product name: InertCap1, manufactured by GL Sciences)

[0394] Length: 60m, inner diameter: 0.25mm, film thickness: 1.50μm

[0395] Injection volume: 1.0 μL

[0396] Gasification chamber temperature: 280℃

[0397] Column oven temperature: When analyzing a composition containing glycidyl methacrylate, keep it at 150°C for 1 minute, increase the temperature from 1500°C to 260°C at 2.5°C / min, and keep it at 260°C for 15 minutes. When analyzing a composition containing methoxyethyl methacrylate, keep it at 60°C for 1 minute, increase the temperature from 60°C to 260°C at 5°C / min, and keep it at 260°C for 9 minutes.

[0398] Carrier gas: Helium

[0399] Injection mode: split (split ratio 25)

[0400] Control mode: Constant linear speed (35.0 cm / s)

[0401] Pressure: 262.8kPa

[0402] Total flow rate: 47.2mL / min

[0403] Purge flow rate: 3.0mL / min

[0404] Column flow rate: 1.70mL / min

[0405] (MS conditions)

[0406] Ionization method: EI (Electron Ionization)

[0407] Ion source temperature: 200°C

[0408] Interface temperature: 300℃

[0409] m / z detection range: 30~600

[0410] Detection time: 50 minutes for analysis of the composition containing glycidyl methacrylate, and 60 minutes for analysis of the composition containing methoxyethyl methacrylate.

[0411] [Water content]

[0412] The moisture content was quantitatively determined by the Karl Fischer method using a trace moisture measuring device (product name: CA-200, manufactured by Nitto Seiko Analytical Science Co., Ltd.).

[0413] [Example C1]

[0414] Liquid A was prepared by adding 0.0222 g of 1-octane as component A to 10.0085 g of glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 174 mass ppm).

[0415] Separately, 0.0214 g of 2,4-dimethyl-6-tert-butylphenol as component B was added to 10.0147 g of GMA (water content: 174 mass ppm) to prepare liquid B.

[0416] Next, 0.0337 g of liquid A and 0.0309 g of liquid B were added to 5.0003 g of GMA (water content: 174 mass ppm) to prepare a composition containing an ester compound.

[0417] After the obtained composition containing an ester compound was stored at 25°C for 21 days, the GMA purity (%) was calculated from the ratio (area %) of the area value of GMA to the total area values ​​of all components detected by GC-MS measurement. In the calculation, the value obtained by subtracting the water content (mass %) from 100% was multiplied by the area % of each component.

[0418] [Examples C2 to C9, Comparative Examples C1 to C3]

[0419] Except that the compositions of liquid A, liquid B, and the composition containing an ester compound were changed as shown in Table 9, a composition containing an ester compound was prepared in the same manner as in Example C1, and the GMA purity was determined.

[0420] [Table 9]

[0421]

[0422] The abbreviations in Table 9 have the following meanings. GMA: glycidyl methacrylate Oct: 1-octene

[0423] 2EH: 2-ethyl-1-hexene

[0424] Ddc: 1-dodecene

[0425] DMTBP: 2,4-dimethyl-6-tert-butylphenol

[0426] 4MP: 4-methoxyphenol

[0427] IPPPD: N-isopropyl-N'-phenyl-p-phenylenediamine

[0428] PHT: Phenothiazine

[0429] HO-TEMPO: 4-Hydroxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl radical

[0430] Table 10 shows the measurement results of the GMA purity in each example.

[0431] [Table 10]

[0432] [Table 10]

[0433]

[0434] As shown in Table 10, the ester compound-containing compositions of Examples C1 to C9 containing Component A showed less production of GMA dimer and glycidyl pyruvate after storage and had higher GMA purity than the ester compound-containing compositions of Comparative Examples C1 to C2 not containing Component A.

[0435] [Examples C10 to C12, Comparative Examples C4 to C6]

[0436] The composition containing an ester compound was prepared in the same manner as in Example C1 except that 2-methoxyethyl methacrylate (MTMA, manufactured by Tokyo Chemical Industry, water content 575 mass ppm) was used instead of GMA, and the compositions of liquid A, liquid B, and the composition containing an ester compound were changed as shown in Table 11. The amount of MTMA dimer generated and the MTMA purity were determined. The amount of MTMA dimer generated (mass %) was determined from the ratio (area %) of the area value of ETMA dimer to the total area value of all components detected. The results are shown in Table 12.

[0437] [Table 11]

[0438]

[0439] [Table 12]

[0440] [Table 12]

[0441]

[0442] As shown in Table 12, the ester compound-containing compositions of Examples C10 to C12 containing Component A had less MTMA dimer formation after storage and higher MTMA purity than the ester compound-containing compositions of Comparative Examples C4 to C6 not containing Component A.

[0443] [Example D1]

[0444] A mixture of butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry, water content 164 mass ppm) and ethyl methacrylate (EMA, manufactured by Tokyo Chemical Industry, water content 245 mass ppm) was used as the ester compound, 1-octene was used as component A, and 2,4-dimethyl-6-tert-butylphenol was used as component B. A composition containing an ester compound was prepared in the same manner as in Example A1 except that the composition of the composition containing the ester compound was changed as shown in Table 13, and the amount of BMA dimer generated, BMA purity, and EMA purity were determined. The results are shown in Table 13.

[0445] The BMA purity (%) was calculated from the ratio (area %) of the area value of BMA to the total area value of all components detected, and the EMA purity (%) was calculated from the ratio (area %) of the area value of EMA to the total area value of all components detected. In the calculation of BMA dimer, BMA purity and EMA purity, the value obtained by subtracting the water content (mass %) from 100% was multiplied by the area % of each component.

[0446] [Comparative Examples D1 to D2]

[0447] A composition containing an ester compound was prepared in the same manner as in Example D1 except that the composition of the composition containing an ester compound was changed as shown in Table 13, and the amount of BMA dimer generated, BMA purity, and EMA purity were determined.

[0448] [Table 13]

[0449]

[0450] As shown in Table 13, the ester compound-containing composition of Example D1 containing Component A had a smaller amount of BMA dimer generated after storage and a higher BMA purity than the ester compound-containing compositions of Comparative Examples D1 to D2 not containing Component A.

[0451] [Example D2]

[0452] Butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry, water content 164 mass ppm) was used as the ester compound, 1-octene was used as component A, and 2,4-dimethyl-6-tert-butylphenol was used as component B. A composition containing an ester compound was prepared in the same manner as in Example A1 except that the composition of the composition containing the ester compound was changed as shown in Table 14, and the amount of BMA dimer generated and the BMA purity were determined. The results are shown in Table 14.

[0453] [Examples D3 to D4]

[0454] A composition containing an ester compound was prepared in the same manner as in Example D2 except that the composition of the composition containing an ester compound was changed as shown in Table 14 by adding methanol (manufactured by Nacalai Tesque, for high performance liquid chromatography), and the amount of BMA dimer produced and the BMA purity were determined. The results are shown in Table 14.

[0455] [Table 14]

[0456] [Table 14]

[0457]

[0458] As shown in Table 14, when the compositions containing ester compounds of Examples D3 and D4, which contain component A and have the same BMA concentration, are compared, the amounts of BMA dimer generated are similar in Example D3, which uses component A and component B, and Example D4, which uses only component A. On the other hand, the composition containing ester compounds of Example D2, which contains component A and has a high BMA concentration, has a smaller amount of BMA generated than the composition containing ester compounds of Example D3, which contains component A and has a low BMA concentration.

[0459] [Example D5]

[0460] Butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry, water content 164 mass ppm) was used as the ester compound, 1-octene was used as component A, and 2,4-dimethyl-6-tert-butylphenol was used as component B. A composition containing an ester compound was prepared in the same manner as in Example A1 except that the composition of the composition containing the ester compound was changed as shown in Table 15, and the amount of BMA dimer generated and the BMA purity were determined. The results are shown in Table 15.

[0461] [Example D6, Comparative Example D3]

[0462] A composition containing an ester compound was prepared in the same manner as in Example D2 except that the composition of the composition containing an ester compound was changed as shown in Table 15, and the amount of BMA dimer produced and the BMA purity were determined. The results are shown in Table 15.

[0463] [Table 15]

[0464] [Table 15]

[0465]

[0466] As shown in Table 15, the ester compound-containing compositions of Examples D5 and D6 containing an appropriate amount of Component A showed less BMA dimer generation after storage and higher BMA purity than the ester compound-containing composition of Comparative Example D3 containing an excessive concentration of Component A.

[0467] [Example D7]

[0468] Butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry, water content 164 mass ppm) was used as the ester compound, 1-octene was used as component A, and 2,4-dimethyl-6-tert-butylphenol was used as component B. A composition containing an ester compound was prepared in the same manner as in Example A1 except that the composition of the composition containing the ester compound was changed as shown in Table 16, and the amount of BMA dimer generated was determined. The results are shown in Table 16.

[0469] [Example D8, Comparative Example D4]

[0470] A composition containing an ester compound was prepared in the same manner as in Example D2 except that the composition of the composition containing an ester compound was changed as shown in Table 16, and the amount of BMA dimer produced was determined. The results are shown in Table 16.

[0471] [Table 16]

[0472] [Table 16]

[0473]

[0474] As shown in Table 16, the ester compound-containing compositions of Examples D7 and D8 containing Component A and having a water content of a predetermined amount or less also produced less BMA dimer after storage than the ester compound-containing composition of Comparative Example D4 having an excessive water content.

[0475] Industrial Applicability

[0476] According to the present invention, a composition containing an ester compound that can be used as a raw material for a (meth)acrylic acid-based polymer can be stably stored for a long period of time, and the composition is industrially useful.

Claims

1. A composition containing an ester compound, comprising an ester compound (1) represented by the following formula (1) and an α-olefin as component A, The content of the component A is 1 ppm to 1500 ppm by mass, The moisture content of the composition is 5000 ppm by mass or less, CH2=CR 1 -C(=O)-O-R 2 ···(1) in, In the formula (1), R 1 is a hydrogen atom or a methyl group, R 2 It is a hydrocarbon group having 2 to 20 carbon atoms which may have a hetero atom and may have a functional group.

2. The composition containing an ester compound according to claim 1, wherein In the formula (1), R 2 A hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxyl group, a linear or branched alkyl group having 2 to 8 carbon atoms or a group in which one or two hydrogen atoms of a hydroxyalkyl group are substituted with a (meth)acryloyloxy group, or a group having an ethereal oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

3. The composition containing an ester compound according to claim 1, wherein The ester compound (1) comprises an ester compound (1-1) represented by the following formula (1-1): CH2=CR a1 -C(=O)-O-R a2 ···(1-1) Among them, in the formula (1-1), R a1 is a hydrogen atom or a methyl group, R a2 It is a hydrocarbon group having 2 to 20 carbon atoms.

4. The composition containing an ester compound according to claim 3, wherein Contains the R a2 The ester compound (1-1) is a linear or branched alkyl group having 2 to 20 carbon atoms.

5. The composition containing an ester compound according to claim 3, wherein The content of the ester compound (1-1) is 85.00% by mass to 99.99% by mass.

6. The composition containing an ester compound according to claim 1, wherein The ester compound (1) comprises one or more ester compounds (1-2) selected from the group consisting of an ester compound (1-21) represented by the following formula (1-21), an ester compound (1-22) represented by the following formula (1-22), and an ester compound (1-23) represented by the following formula (1-23). Among the formulas (1-21) to (1-23), R b1 , R b3 , R b5 , R b6 , R b8 and R b9 are each independently a hydrogen atom or a methyl group, R b2 and R b4 are each independently a linear or branched alkylene or hydroxyalkylene group having 2 to 8 carbon atoms, R b7 It is a linear or branched trivalent hydrocarbon group having 2 to 8 carbon atoms.

7. The composition containing an ester compound according to claim 6, wherein The ester compound (1-2) includes one or more selected from the group consisting of ethylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and trimethylolpropane tri(meth)acrylate.

8. The composition containing an ester compound according to claim 6, wherein The content of the ester compound (1-2) is 85.00% by mass to 99.99% by mass.

9. The composition containing an ester compound according to claim 1, wherein The ester compound (1) includes an ester compound (1-3) represented by the following formula (1-3): CH2=CR c1 -C(=O)-O-R c2 ···(1-3) Among them, in the formula (1-3), R c1 is a hydrogen atom or a methyl group, R c2 A group having an etheric oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

10. The composition containing an ester compound according to claim 9, wherein Contains the R c2 The ester compound (1-3) is 2-methoxyethyl, glycidyl or tetrahydrofurfuryl.

11. The composition containing an ester compound according to claim 9, wherein The content of the ester compound (1-3) is 85.00% by mass to 99.99% by mass.

12. The composition containing an ester compound according to claim 1, wherein The component A contains an α-olefin having 6 to 12 carbon atoms.

13. The composition containing an ester compound according to claim 1, wherein It further contains component B, a polymerization inhibitor. The composition containing an ester compound according to claim 1 , which is a composition containing an ester compound that can be stored for one day or more.

15. A method for producing a composition containing an ester compound, the composition containing an ester compound comprising an ester compound (1) represented by the following formula (1): The production method comprises the following steps: performing an ester exchange reaction between methyl (meth)acrylate and an alcohol (a) having 2 to 20 carbon atoms in the presence of component A, i.e., an α-olefin; CH2=CR 1 -C(=O)-O-R 2 ···(1) in, In the formula (1), R 1 is a hydrogen atom or a methyl group, R 2 It is a hydrocarbon group having 2 to 20 carbon atoms which may have a hetero atom and may have a functional group.

16. The method for producing a composition containing an ester compound according to claim 15, wherein in the formula (1), R 2 a hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxyl group, a linear or branched alkyl group having 2 to 8 carbon atoms or a group in which one or two hydrogen atoms of a hydroxyalkyl group are substituted with a (meth)acryloyloxy group, or a group having an ethereal oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms, The alcohol (a) is at least one selected from the following alcohols (a1) to (a3), (a1) Monohydric alcohol having 2 to 20 carbon atoms (a2) at least one alcohol selected from diols having 2 to 8 carbon atoms and triols having 2 to 8 carbon atoms (a3) Alcohols having 2 to 8 carbon atoms and containing an ether bond.

17. The method for producing a composition containing an ester compound according to claim 16, wherein In the presence of the component A, methyl (meth)acrylate and the alcohol (a1) are subjected to an ester exchange reaction to obtain an ester compound (1-1) represented by the following formula (1-1), CH2=CR a1 -C(=O)-O-R a2 ···(1-1) Among them, in the formula (1-1), R a1 is a hydrogen atom or a methyl group, R a2 It is a hydrocarbon group having 2 to 20 carbon atoms.

18. The method for producing a composition containing an ester compound according to claim 17, wherein The alcohol (a1) includes a linear or branched monohydric alcohol having 2 to 20 carbon atoms.

19. The method for producing a composition containing an ester compound according to claim 16, wherein An ester compound (1-2) comprising one or more ester compounds (1-2) selected from the group consisting of an ester compound (1-21) represented by the following formula (1-21), an ester compound (1-22) represented by the following formula (1-22), and an ester compound (1-23) represented by the following formula (1-23) is obtained by performing an ester exchange reaction between methyl (meth)acrylate and the alcohol (a2) in the presence of the component A. Among the above formulas (2-1) to (2-3), R b1 , R b3 , R b5 , R b6 , R b8 and R b9 are each independently a hydrogen atom or a methyl group, R b2 and R b4 are each independently a linear or branched alkylene or hydroxyalkylene group having 2 to 8 carbon atoms, R b7 It is a linear or branched trivalent hydrocarbon group having 2 to 8 carbon atoms.

20. The method for producing a composition containing an ester compound according to claim 19, wherein The alcohol (a2) includes one or more selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and trimethylolpropane.

21. The method for producing a composition containing an ester compound according to claim 16, wherein In the presence of the component A, methyl (meth)acrylate and the alcohol (a3) ​​are subjected to an ester exchange reaction to obtain an ester compound (1-3) represented by the following formula (1-3), CH2=CR c1 -C(=O)-O-R c2 ···(1-3) Among them, in the formula (1-3), R c1 is a hydrogen atom or a methyl group, R c2 A group having an etheric oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

22. The method for producing a composition containing an ester compound according to claim 21, wherein The alcohol (a3) ​​includes one selected from the group consisting of 2-methoxyethanol, glycidyl alcohol, and tetrahydrofurfuryl alcohol.

23. The method for producing a composition containing an ester compound according to any one of claims 15 to 22, wherein The component A contains an α-olefin having 6 to 12 carbon atoms. 24 . A polymerizable composition for producing a (meth)acrylic polymer, comprising the composition containing an ester compound according to claim 1 .

25. The polymerizable composition according to claim 24, wherein The content of component C, i.e., at least one compound selected from compounds of transition metals and compounds of Group IIIA elements, is 7×10 4 Mass ppm or less.

26. A method for producing a (meth)acrylic polymer, comprising the step of polymerizing the polymerizable composition according to claim 24.

27. A method for producing a (meth)acrylic polymer, comprising the step of polymerizing the polymerizable composition according to claim 25.

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