Patent Application
20240059818
The present invention relates to a methyl methacrylate-containing composition and a method of producing methyl methacrylate polymer.
Methyl methacrylate (hereinafter also referred to as “MMA”) is known to be an extremely useful substance used as a raw material of various applications and types of polymers. For example, polymethyl methacrylate, a homopolymer of methyl methacrylate, is used in signboards, lighting equipment, automotive parts, construction-related materials, light guiding panels for flat displays, light diffusion plates, and the like, taking advantage of its excellent transparency, weather resistance, and other properties. In addition, copolymers of methyl methacrylate and other monomers are used in paints, adhesives, resin modifier, artificial marble, latices for paper, and the like. Various methods have been developed for industrially producing methyl methacrylate, and for example, the acetone cyanohydrin (ACH) method, the new acetone cyanohydrin (new ACH) method, the C4 direct oxidation method, the direct methyl esterification method, the ethylene method, and the new ethylene method are known (Non-Patent Document 1). In these production methods, methyl methacrylate of a quality suitable for the intended use is obtained by performing purification such as distillation to remove unreacted raw materials and by-products contained in the produced methyl methacrylate.
Since methyl methacrylate has a tendency to polymerize, it is known that the quality of methyl methacrylate is maintained by adding a polymerization inhibitor when producing methyl methacrylate or storing produced methyl methacrylate (Non-Patent Document 2). For example, Patent Document 1 describes that methyl ether of hydroquinone (MEHQ) is particularly preferable among various polymerization inhibitors. Patent Document 2 describes that N,N′-dialkyl-p-phenylenediamine and N-oxyl are preferable among various polymerization inhibitors. Patent Document 3 describes distillation of methyl methacrylate in the presence of a phenol polymerization inhibitor. Patent Document 4 describes use of a diphenylamine derivative as a polymerization inhibitor. Patent Document 5 describes use of a benzene triamine derivative as a polymerization inhibitor.
Patent Document 1: JP 2004-155757 A
Patent Document 2: JP 2005-502695 A
Patent Document 3: JP H10-504553 A
Patent Document 4: JP 2002-533309 A
Patent Document 5: JP 2002-513034 A
Non-Patent Document 1: Toru Kuroda, “Development of Catalyst for Producing Methyl Methacrylate”, Catalysts & Catalysis, 45 (5), 366-371, 2003, Catalysis Society of Japan
Non-Patent Document 2: Takayuki Otsu, “On the Functions of Polymerization Inhibitors”, Synthetic Organic Chemistry, 33 (8), 634-640, 1975, The Society of Synthetic Organic Chemistry, Japan
However, even in cases where polymerization inhibitors as described above are added, the quality of methyl methacrylate may deteriorate during storage. In view of the above circumstances, the purpose of the present invention is to provide a methyl methacrylate-containing composition with high quality stability during storage.
In order to achieve the above purposes, the present inventors have intensively studied. As a result, they found that, in methyl methacrylate with the quality deteriorated during storage, the concentration of methyl methacrylate is reduced, and methyl methacrylate dimers and methyl pyruvate are produced. The presence of methyl methacrylate dimers in methyl methacrylate may change the structure of methyl methacrylate polymer obtained by polymerization to adversely affect its physical properties. Furthermore, the presence of methyl pyruvate in methyl methacrylate causes coloration of methyl methacrylate polymer obtained by polymerization. The present inventors have found that inclusion of an α,β-unsaturated carbonyl compound represented by a specific structural formula in a methyl methacrylate-containing composition results in improved quality stability during storage, and reduced production of methyl methacrylate dimers and methyl pyruvate, thereby completing the present invention.
Accordingly, the present invention provides the following [1] to [33]:
according to [16], wherein the MA2 is from 10 to 5,000 μmol/L;
According to the present invention, a methyl methacrylate-containing composition having high quality stability with reduced production of methyl methacrylate dimer and methyl pyruvate during storage can be provided.
Embodiments according to the present invention will be described below, but the present invention is not limited to them.
As used herein, any numerical value range indicated by the term “to” means any range including the numerical values described before and after the term “to” as the lower and upper limit values, respectively, and “A to B” means A or more and B or less.
A methyl methacrylate-containing composition in a first aspect according to the present invention comprises methyl methacrylate, an α,β-unsaturated carbonyl compound represented by the following Formula (1) (component A1), and a polymerization inhibitor (component B), wherein the concentration of methyl methacrylate is from 99 to 99.99% by mass.
In Formula (1) above, R1, R2, and R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, an alkoxy group, an amino group, a monovalent group containing a carbonyl group, an alkylthio group, or an arylthio group. R4 represents an alkyl group, an alkenyl group, an aryl group, a hydroxy group, an alkoxy group, an amino group, a monovalent group containing a carbonyl group, an alkylthio group, or an arylthio group. R1 and R2, R2 and R3, and R3 and R4 each may be linked to each other to form a ring, except when R1=H, R2=H, R3=CH3, and R4=OCH3, that is, when the α, β-unsaturated carbonyl compound represented by Formula (1) is methyl methacrylate. H represents a hydrogen atom, C represents a carbon atom, and O represents an oxygen atom.
The methyl methacrylate-containing composition may also contain other compound (component C) or water as long as the composition satisfies a concentration of methyl methacrylate of from 99 to 99.99% by mass. Each item will be described below in detail.
The methyl methacrylate-containing composition in the first aspect according to the present invention comprises an α,β-unsaturated carbonyl compound represented by Formula (1) described above (component A1). When the component A1 and the component B described later coexist, the production of methyl methacrylate dimers and methyl pyruvate during storage of the methyl methacrylate-containing composition can be repressed. The reason for this is presumed as follows.
Methyl methacrylate dimers are produced due to radicals generated during storage of methyl methacrylate. Examples of the radicals include hydroxyl radicals produced when oxygen molecules absorb ultraviolet light derived from sunlight. Hydroxyl radicals also cause the production of methyl pyruvate due to oxidation of methyl methacrylate. The α, β-unsaturated carbonyl compound has a conjugated double bond, and thus absorbs ultraviolet light. The absorption wavelength varies depending on the type of the substituent. The α, β-unsaturated carbonyl compound having a structure represented by Formula (1) described above can absorb ultraviolet light across a broad wavelength. Therefore, when the methyl methacrylate-containing composition comprises a component A1, a broad wavelength of ultraviolet light is absorbed, and the production of hydroxyl radicals is reduced. Further, by including the component B described later, it is possible to trap generated hydroxyl radicals. Thus, it is considered that when the component A1 and the component B coexist, the production of methyl methacrylate dimers and methyl pyruvate can be reduced. Among various organic compounds that absorb ultraviolet light, an α, β-unsaturated carbonyl compound has a molecular structure that is similar to that of methyl methacrylate, so that when producing a polymer using the methyl methacrylate-containing composition as a raw material, adverse effects due to inclusion of an α, β-unsaturated carbonyl compound as an impurity can be reduced.
The molecular weight of the component A1 is preferably 1,000 or less. When the molecular weight is 1,000 or less, the number of conjugated double bonds per unit mass in the component Al can be increased, so that the effect of the present invention can be obtained with less mass. The molecular weight of the component Al is more preferably 800 or less, still more preferably 600 or less, and particularly preferably 400 or less.
In Formula (1) above, R1, R2 and R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, an alkoxy group, an amino group, a monovalent group containing a carbonyl group, an alkylthio group, or an arylthio group. R4 in Formula (1) above represents an alkyl group, an alkenyl group, an aryl group, a hydroxy group, an alkoxy group, an amino group, a monovalent group containing a carbonyl group, an alkylthio group, or an arylthio group. R1, R2, R3, and R4 may be the same as or different from each other.
When R1, R2, R3 and R4 satisfy the conditions described above, the π-conjugated system in the component A1 is maintained, and thus the component A1 has a property of absorbing a broad wavelength of ultraviolet light, so that the effect of the present invention can be obtained. R1, R2 and R3 each are preferably a hydrogen atom, a C1-5 alkyl group, a C2-5 alkenyl group, a C1-12 aryl group, a C1-6 alkoxy group, an amino group, a monovalent group containing a carbonyl group, or a C1-5 alkylthio group. They are highly stable substituents, and thus can prevent the component A1 from being changed into other compounds during storage. When the component A1 has such a substituent, an amount of ultraviolet light absorbed by the component A1 as a single molecule will be sufficient. R1, R2 and R3 are more preferably a hydrogen atom or a C1-5 alkyl group, and still more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. R4 is preferably a C1-5 alkyl group, a C2-5 alkenyl group, a C1-12 aryl group, a hydroxy group, a C1-6 alkoxy group, an amino group, a monovalent group containing a carbonyl group, or a C1-5 alkylthio group. They are highly stable substituents, and thus can prevent the component A1 from being changed into other compounds during storage. R4 is more preferably a C1-5 alkyl group or a C1-5 alkoxy group, and still more preferably a methyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, or an isopentoxy group. When R4 is the structure described above, the methyl methacrylate-containing composition can have higher quality stability during storage.
The alkyl group is a chain (linear or branched) alkyl group or a cyclic alkyl group. The alkyl group is preferably a C1-20 alkyl group, more preferably a C1-10 alkyl group, and still more preferably a C1-5 alkyl group. Examples of the chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, an octyl group, a decyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group; and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
The alkenyl group is a chain (linear or branched) alkenyl group or a cyclic alkenyl group. The alkenyl group is preferably a C2-20 alkenyl group, more preferably a C2-10 alkenyl group, and still more preferably a C2-5 alkenyl group. Examples of the chain alkenyl group include a vinyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and 2-hexenyl group. Examples of the cyclic alkenyl group include a cyclopentenyl group and a cyclohexenyl group.
The aryl group is preferably a C1-20 aryl group, and more preferably a C1-12 aryl group. The aryl group include a heteroaryl group containing oxygen, nitrogen, sulfur, or the like. Examples of the aryl group include a phenyl group, a mesityl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 2-ethylphenyl group, an isoxazolyl group, an isothiazolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a thiadiazolyl group, a thienyl group, a triazolyl group, a tetraazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazolyl group, a pyrrolyl group, a furyl group, a furazanyl group, an isoquinolyl group, an isoindolyl group, an indolyl group, a quinolyl group, a pyridothiazolyl group, a benzimidazolyl group, a benzooxazolyl group, a benzothiazolyl group, a benzotriazolyl group, a benzofuranyl group, an imidazopyridinyl group, a triazopyridinyl group, and a purinyl group.
The alkoxy group is preferably a C1-20 alkoxy group, more preferably a C1-10 alkoxy group, and still more preferably a C1-6 alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, an isopentoxy group, and a phenoxy group.
The amino group includes an amino group without a substituent on the nitrogen atom (—NH2), and an amino group in which some or all of the hydrogen atoms bound to the nitrogen atom are substituted with carbon atoms. The number of carbon atoms in an amino group substituted with carbon atoms is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 5. Examples of the amino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a dimethylamino group, a diethylamino group, an anilino group, a toluidino group, an anisidino group, a diphenylamino group, and an N-methyl-N-phenylamino group.
Examples of the monovalent group containing a carbonyl group include a formyl group, an acyl group, a carboxy group, an amide group, an alkoxy carbonyl group, a thiocarboxy group, and a thioester group.
The acyl group is a substituent in which a carbonyl group is linked with an alkyl group, an alkenyl group, or an aryl group. The total number of carbon atoms derived from a carbonyl group (one) and derived from an alkyl group, alkenyl group, or an aryl group is preferably from 2 to 20, more preferably from 2 to 10, and still more preferably from 2 to 6. Examples of the acyl group include an acetyl group, a propionyl group, a butylcarbonyl group, a vinylcarbonyl group, and a benzoyl group.
The amide group include an amide group without a substituent on the nitrogen atom (—CONH2), and an amide group in which some or all of the hydrogen atoms bound to the nitrogen atom are substituted with carbon atoms. The number of carbon atoms in the amide group, which is the total number of carbon atoms derived from a carbonyl group (one) and the number of carbon atoms substituted on the nitrogen atom, is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 5. Examples of the amide group include an unsubstituted amide group, an N-methylamide group, an N-ethylamide group, an N-phenylamide group, an N,N-dimethylamide group, and an N-methyl-N-phenylamide group.
The alkoxy carbonyl group is a substituent in which a carbonyl group and an alkoxy group are linked, and also referred to as ester group. The total number of carbon atoms derived from a carbonyl group (one) and derived from an alkoxy group is preferably from 2 to 20, more preferably from 2 to 10, and still more preferably from 2 to 6. Examples of the alkoxy carbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group.
The thioester group is a substituent in which a carbonyl group and an alkylthio group or an arylthio group are linked. The total number of carbon atoms derived from a carbonyl group (one) and derived from an alkylthio group or an arylthio group is preferably from 2 to 20, more preferably from 2 to 10, and still more preferably from 2 to 6. Examples of the thioester group include a methylthiocarbonyl group, an ethylthiocarbonyl group, a butylthiocarbonyl group, and a phenylthiocarbonyl group.
The monovalent group containing a carbonyl group may be a substituent in which one or more hydrogen(s) in an alkyl group is/are substituted with a carbonyl group(s). Examples of such a substituent include a 2-acetoxyethyl group, a 2-acetoethyl group, and a 2-(acetoacetoxy) ethyl group.
The alkylthio group is preferably a C1-20 alkylthio group, more preferably a C1-10 alkylthio group, and still more preferably a C1-5 alkylthio group. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and an isopropylthio group.
The arylthio group is preferably a C1-20 arylthio group, more preferably a C3-10 arylthio group, and still more preferably a C6-10 arylthio group. Examples of the arylthio group include a phenylthio group, and a tolylthio group.
R1 and R2, R2 and R3, and R3 and R4 each may be linked to each other to form a ring. Examples of the compound in which R1 and R2 are linked to form a ring include methyl 2-cyclohexylidenepropionate, and methyl 2-cyclopentylidenepropionate. Examples of the compound in which R2 and R3 are linked to form a ring include methyl 1-cyclohexene-1-carboxylate, and methyl 1-cyclopentene-1-carboxylate. Examples of the compound in which R3 and R4 are linked to form a ring include α-methylene-δ-valerolactone, and α-methylene-γ-butyrolactone.
Among compounds that satisfy the conditions described above, the component A1 is preferably methyl acrylate, butyl acrylate, ethyl methacrylate, methyl crotonate, methyl cis-crotonate, isobutyl methacrylate, butyl methacrylate, propyl methacrylate, isopentyl methacrylate, methyl 2-methylene-3-butenoate, methyl 3,3-dimethylacrylate, methyl 2-ethylacrylate, methyl 2-pentenoate, methyl cinnamate, methyl 3-methoxyacrylate, dimethyl fumarate, methacrylamide, acrylic acid, methacrylic acid, crotonic acid, cis-crotonic acid, 3,3-dimethylacrylic acid, 2-ethylacrylic acid, 2-methylene-3-butenoic acid, trans-3-hexen-2-one, isopropenyl methyl ketone, methyl 2-cyclohexylidenepropionate, methyl 2-cyclopentylidenepropionate, methyl 1-cyclohexene-1-carboxylate, methyl 1-cyclopentene-1-carboxylate, α-methylene-δ-valerolactone, α-methylene-γ-butyrolactone, or isopropenyl methyl ketone, more preferably methyl acrylate, butyl acrylate, ethyl methacrylate, methyl crotonate, methyl cis-crotonate, isobutyl methacrylate, butyl methacrylate, propyl methacrylate, isopentyl methacrylate, methyl 2-methylene-3-butenoate, methyl 3,3-dimethylacrylate, methyl 2-ethylacrylate, methyl 2-pentenoate, methyl cinnamate, methyl 3-methoxyacrylate, dimethyl fumarate, methyl 1-cyclohexene-1-carboxylate, methacrylamide, acrylic acid, methacrylic acid, crotonic acid, cis-crotonic acid, 3,3-dimethylacrylic acid, 2-ethylacrylic acid, 2-methylene-3-butenoic acid, trans-3-hexen-2-one, or isopropenyl methyl ketone, and still more preferably methyl acrylate, ethyl methacrylate, methyl crotonate, isobutyl methacrylate, butyl methacrylate, propyl methacrylate, isopentyl methacrylate, methyl 3,3-dimethylacrylate, and isopropenyl methyl ketone from the viewpoint of quality stability of methyl methacrylate-containing composition during storage.
One or two or more component(s) A1 may be contained in the methyl methacrylate-containing composition in the first aspect according to the present invention.
The methyl methacrylate-containing composition in a first aspect according to the present invention comprises a polymerization inhibitor (component B). As used herein, the term “polymerization inhibitor” means a compound having a function to inhibit the polymerization reaction of methyl methacrylate. Examples of the polymerization inhibitor include a phenol compound, a quinone compound, a nitrobenzene compound, an N-oxyl compound, an amine compound, a phosphorus-containing compound, a sulfur-containing compound, an iron-containing compound, a copper-containing compound, and a manganese-containing compound. When the component B is included, the progress of the polymerization reaction of methyl methacrylate via a radical polymerization mechanism during storage of methyl methacrylate can be repressed. The component B can also trap the hydroxyl radicals generated during storage of methyl methacrylate. That is, when the methyl methacrylate-containing composition comprises the component A1 as well as a component B, the hydroxyl radical content can be reduced via two different mechanisms, one in which the component A1 can reduce production of hydroxyl radicals, and the other in which the component B can remove produced hydroxyl radicals. Thus, it is considered that the production of methyl methacrylate dimers and methyl pyruvate can be efficiently reduced.
Examples of the polymerization inhibitor that is a phenol compound include alkylphenol, hydroxyphenol, aminophenol, nitrophenol, nitrosophenol, alkoxyphenol, and tocopherol.
Examples of the alkylphenol include o-cresol, m-cresol, p-cresol, 2-t-butyl-4-methylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2-t-butylphenol, 4-t-butylphenol, 2,4-di-t-butylphenol, 2-methyl-4-t-butylphenol, 4-t-butyl-2,6-dimethylphenol, 2,2′-methylene-bis(6-t-butyl-4-methylphenol), 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 4,4′-thiobis(3-methyl-6-t-butylphenol), and 3,5-di-t-butyl-4-hydroxytoluene.
Examples of the hydroxyphenol include hydroquinone, 2-methylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,6-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butylmethoxyhydroquinone, 2,3,5-trimethylhydroquinone, 2,5-dichlorohydroquinone, 1,2-dihydroxybenzene, 2-acetylhydroquinone, 4-methylcatechol, 4-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, and 2,3-dihydroxyacetophenone.
Examples of the aminophenol include o-aminophenol, m-aminophenol, p-aminophenol, 2-(N,N-dimethylamino)phenol, and 4-(ethylamino)phenol.
Examples of the nitrophenol include o-nitrophenol, m-nitrophenol, p-nitrophenol, and 2,4-dinitrophenol.
Examples of the nitrosophenol include o-nitrosophenol, m-nitrosophenol, p-nitrosophenol, and α-nitroso-β-naphthol.
Examples of the alkoxyphenol include 2-methoxyphenol, 2-ethoxyphenol, 2-isopropoxyphenol, 2-t-butoxyphenol, 4-methoxyphenol, 4-ethoxyphenol, 4-propoxyphenol, 4-butoxyphenol, 4-t-butoxyphenol, 4-heptoxyphenol, hydroquinone monobenzyl ether, t-butyl-4-methoxyphenol, di-t-butyl-4-methoxyphenol, pyrogallol-1,2-dimethylether, and hydroquinone monobenzoate.
Examples of the tocopherol include α-tocopherol, and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran.
Examples of the polymerization inhibitor that is a quinone 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.
Examples of the polymerization inhibitor that is a nitrobenzene compound include nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrotoluene, dinitrodurene, and 2,2-diphenyl-1-picrylhydrazyl.
Examples of the polymerization inhibitor that is an N-oxyl compound include 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethyl-piperidine-N-oxyl, piperidine-1-oxyl, 4-(dimethylamino)-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-amino-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-ethanoloxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,5,5-tetramethyl-piperidine-N-oxyl, 3-amino-2,2,5,5-tetramethyl-piperidine-N-oxyl, 4,4′,4″-tris(2,2,6,6-tetramethyl-piperidine-N-oxyl)phosphite, 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl, pyrrolidine-1-oxyl, 2,2,5,5-tetramethyl-1-oxa-3-azacyclopentyl-3-oxy, 2,2,5,5-tetramethyl-3-pyrrolinyl-1-oxy-3-carboxylic acid, 2,2,3,3,5,5,6,6-octamethyl-1,4-diazacyclohexyl-1,4-dioxy, di-tert-butylnitroxide, and di-tert-amylnitroxide.
Examples of the polymerization inhibitor that is an amine compound include N,N-diphenylamine, alkylated diphenylamine, 4,4′-dicumyl-diphenylamine, 4,4′-dioctyldiphenylamine, 4-aminodiphenylamine, p-nitrosodiphenylamine, N-nitrosodinaphthylamine, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosophenylhydroxylamine, N,N′-dialkyl-p-phenylenediamine (the alkyl groups may be the same or different, and may each independently comprise 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-benzenediamine, N-(1,4-dimethylpentyl)-N′-phenyl-1,4-benzenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-1,4-benzenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, aldol-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, and 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine.
Examples of the polymerization inhibitor that is a 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, phosphonic acid [1,1-diphenyl-4,4′-diylbistetrakis-2,4-bis(1,1-dimethylethyl)phenyl] ester, triphenyl phosphite, tris(nonylphenyl) phosphite, 4,4′-isopropylidenediphenol alkyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(biphenyl) phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphate, di(nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol-A pentaerythritol diphosphite, tetra(tridecyl)-4,4′-butylidenebis(3-methyl-6-tert-butylphenol)diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester, sodium-bis(4-tert-butylphenyl) phosphate, sodium-2,2′-methylene -bis(4,6-di-tert-butylphenyl)phosphate, and 1,3-bis(diphenoxyphosphonyloxy)benzene.
Examples of the polymerization inhibitor that is a 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, 3,7-bis(dimethylamino)phenothiazinium chloride, and sulfur (simple substance).
Examples of the polymerization inhibitor that is an iron-containing compound include iron (III) chloride.
Examples of the polymerization inhibitor that is a copper-containing compound include copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, copper acetate, copper thiocyanate, copper nitrate, copper chloride, copper carbonate, copper hydroxide, copper acrylate, and copper methacrylate.
Examples of the polymerization inhibitor that is a manganese-containing compound include manganese dialkyl dithiocarbamate (the alkyl groups are each any of a methyl group, an ethyl group, a propyl group, and a butyl group, and may be the same or different), manganese diphenyl dithiocarbamate, manganese formate, manganese acetate, manganese octanoate, manganese naphthenate, manganese permanganate, and ethylenediaminetetraacetic acid manganese salt.
Among those described above, the component B is preferably at least one polymerization inhibitor(s) selected from the group consisting of a phenol compound, an N-oxyl compound, an amine compound, a phosphorus-containing compound, and a sulfur-containing compound, and more preferably at least one polymerization inhibitor(s) selected from the group consisting of hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, N,N-diphenylamine, N-nitrosodiphenylamine, triphenyl phosphite, and phenothiazine, from the viewpoint of quality stability of the methyl methacrylate-containing composition during storage.
One or two or more component(s) B may be contained.
In cases where the methyl methacrylate-containing composition comprises a compound that corresponds to both components A1 and B, the compound is considered as the component B. Thus, the methyl methacrylate-containing composition must comprise the component A1 other than the compound. In cases where two or more compounds that correspond to both components A1 and B are contained, the compound with the highest molar concentration in the methyl methacrylate composition is considered as a component B, and the other compound(s) is/are considered as the component(s) A1.
When the concentration of the component A1 is MA1 (μmol/L) and the concentration of the component B is MB (μmol/L), MB/MA1 is preferably 0.1 or more from the viewpoint of efficiency in reducing the production of methyl pyruvate. The upper limit of MB/MA1 is not particularly limited, and is usually 100 or less.
MA1 is preferably from 1 to 85,000 μmol/L. When MA1 is 1 μmol/L or more, the effect of reducing the production of methyl methacrylate dimer and methyl pyruvate can be sufficiently obtained. When MA1 is 85,000 μmol/L or less, the impurity content after production of methyl methacrylate polymer by polymerization of the methyl methacrylate-containing composition according to the present invention is reduced, so that adverse effects on physical properties of the polymer can be prevented. The lower limit of MA1 is more preferably 10 μmol/L or more, and still more preferably 50 μmol/L or more. The upper limit of MA1 is more preferably 40,000 μmol/L or less, still more preferably 20,000 μmol/L or less, and particularly preferably 15,000 μmol/L or less.
MB is preferably from 1 to 7,000 μmol/L. When MB is 1 μmol/L or more, the effect of reducing the production of methyl methacrylate dimer and methyl pyruvate can be sufficiently obtained. When MB is 7,000 μmol/L or less, the impurity content after production of methyl methacrylate polymer by polymerization of the methyl methacrylate-containing composition according to the present invention is reduced, so that adverse effects on physical properties of the polymer can be prevented. The lower limit of MB is more preferably 10 μmol/L or more, and still more preferably 40 μmol/L or more. The upper limit of MB is more preferably 5,000 μmol/L or less, and still more preferably 1,000 μmol/L or less.
The concentration of methyl methacrylate in the methyl methacrylate-containing composition in the first aspect according to the present invention is from 99 to 99.99% by mass. When the concentration of methyl methacrylate is 99% by mass or more, the impurity content after production of methyl methacrylate polymer by polymerization of the methyl methacrylate-containing composition is reduced, so that adverse effects on physical properties of the polymer can be prevented. When the concentration of methyl methacrylate is 99.99% by mass or less, the purification cost can be reduced. The lower limit of the concentration of methyl methacrylate is preferably 99.8% by mass or more.
The methyl methacrylate-containing composition in the first aspect according to the present invention may contain other compound (component C) as long as the composition satisfies a concentration of methyl methacrylate of from 99 to 99.99% by mass. Examples of the component C include impurities produced during the production of methyl methacrylate. For example, methyl methacrylate may contain diacetyl as an impurity. From the viewpoint of reducing coloration of the methyl methacrylate-containing composition, the concentration of diacetyl is preferably 55 μmol/L or less, more preferably 20 μmol/L or less, still more preferably 10 μmol/L or less, and particularly preferably 1 μmol/L.
Inclusion of the component A1, the component B, the component C, and water by the methyl methacrylate-containing composition can be determined, for example, by GC-MS measurement. When the GC-MS chart of the methyl methacrylate-containing composition has a peak at the same retention time as a reference material for the component A1, and when the m/z value detected in the mass spectrum of the peak corresponds to the exact mass of the component A1, it can be determined that the methyl methacrylate-containing composition contains the component A1. In cases where the reference material of the component A1 is not available, it can be determined that the peak is the component A1 peak when the mass spectrum peak pattern shown in the GC-MS chart of the methyl methacrylate-containing composition corresponds to the mass spectrum pattern of the component A1 recorded in the mass spectrum database. In other words, it can be determined that the methyl methacrylate-containing composition comprises the component A1. Examples of the mass spectrum database include NIST20, NIST17, NIST14, and NIST14s. When detection by GC-MS measurement is impossible due to low volatility, LC-MS can be used for detection. Inclusion of a component B, a component C, and water can also be determined by the same method.
The concentration of methyl methacrylate can be determined, for example, by performing GC-FID measurement of the methyl methacrylate-containing composition, quantifying methyl methacrylate using the area normalization method, and correcting the resulting value using the water concentration determined with a Karl-Fisher moisture meter. The concentration of the component A1 can be determined, for example, by performing GC measurement of the methyl methacrylate-containing composition and using the internal standard method. When the reference material of the component Al is not available, and thus cannot be quantified by the internal standard method, GC-FID measurement for any organic compound having known concentration is performed under the same conditions as the methyl methacrylate-containing composition, and then the concentration of the component A1 can be calculated using the following equation:
In the equation, N is the number of carbon atoms that an organic compound having known concentration contains in one molecule; NA1 is the number of carbon atoms that the component A1 contains in one molecule; SA1 is the peak area of the component A1, S is the peak area of an organic compound having known concentration, and M is the concentration (μmol/L) of an organic component having known concentration.
When quantification by GC measurement is impossible due to low volatility, a chromatography method such as LC can be used for quantification.
The concentrations of the component B and component C can be also determined by the same method as the component A1 described above.
Inclusion of water by the methyl methacrylate-containing composition and its concentration can be determined by the Karl-Fischer method.
A methyl methacrylate-containing composition in a second aspect according to the present invention comprises methyl methacrylate, and an α, β-unsaturated carboxylate ester represented by the following Formula (2) (component A2), wherein the concentration of methyl methacrylate is from 99 to 99.99% by mass. When the concentration of the component A2 is MA2 (μmol/L), MA2 is from 1 to 40,000 μmol/L.
In Formula (2) above, R5, R6, and R7 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, an alkoxy group, an amino group, a monovalent group containing a carbonyl group, an alkylthio group, or an arylthio group. R8 represents an alkyl group, an alkenyl group, or an aryl group. R5 and R6, R6 and R7, and R7 and R8 each may be linked to each other to form a ring, except when R5=H, R6=H, R7=CH3, and R8CH3, that is, when the α, β-unsaturated carbonyl compound represented by Formula (2) is methyl methacrylate. H represents a hydrogen atom, C represents a carbon atom, and O represents an oxygen atom.
The methyl methacrylate-containing composition may also contain the component B, the component C, or water as long as the composition satisfies a concentration of methyl methacrylate of from 99 to 99.99% by mass. Each item will be described in detail.
The methyl methacrylate-containing composition in the second aspect according to the present invention comprises an α, β-unsaturated carboxylate ester represented by Formula (2) described above (component A2). When the methyl methacrylate-containing composition comprises a component A2, because the component A2 as a single molecule can absorb a high amount of ultraviolet light, the production of hydroxyl radicals can be sufficiently reduced. Thus, even in cases where a component B which traps produced hydroxyl radicals is not present, the production of methyl methacrylate dimers and methyl pyruvate can be reduced. However, the methyl methacrylate-containing composition preferably comprises a component B as described above from the viewpoint that the production of methyl methacrylate dimers and methyl pyruvate can be reduced more.
The molecular weight of the component A2 is preferably 1,000 or less. When the molecular weight is 1,000 or less, the number of conjugated double bonds per unit mass can be increased, so that the effect of the present invention can be obtained with less weight. The molecular weight of the component A2 is more preferably 800 or less, still more preferably 600 or less, and particularly preferably 400 or less.
In Formula (2) above, R5, R6, and R7 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, an alkoxy group, an amino group, a monovalent group containing a carbonyl group, an alkylthio group, or an arylthio group. R8 in Formula (2) described above represents an alkyl group, an alkenyl group, or an aryl group. R5, R6, R7, and R8 may be the same as or different from each other.
When R5, R6, R7, and R8 satisfy the conditions described above, the π-conjugated system in the component A2 is maintained, and thus the component A2 has a property of absorbing a broad wavelength of ultraviolet light, so that the effect of the present invention can be obtained. R5, R6, and R7 each are preferably a hydrogen atom, a C1-5 alkyl group, a C2-5 alkenyl group, a C1-12 aryl group, a C1-6 alkoxy group, an amino group, a monovalent group containing a carbonyl group, or a C1-5 alkylthio group. They are highly stable substituents, and thus can prevent the component A2 from being changed into other compounds during storage. When the component A2 has such a substituent, an amount of ultraviolet light absorbed by the component A2 as a single molecule will be suficient. R5, R6, and R7 are more preferably a hydrogen atom or a C1-5 alkyl group, and still more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. R8 is more preferably a C1-5 alkyl group, a C2-5 alkenyl group, or a C1-12 aryl group. They are highly stable substituents, and thus can prevent the component A2 from being changed into other compounds during storage. R8 is more preferably a C1-5 alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or an isopentyl group, and particularly preferably a methyl group. When R8 is the structure described above, the methyl methacrylate-containing composition can have higher quality stability during storage.
In preferred embodiments, the alkyl group, the alkenyl group, the aryl group, the hydroxy group, the alkoxy group, the amino group, the monovalent group containing a carbonyl group, the alkylthio group, the arylthio group, and the like in Formula (2) described above are the same as Formula (1) described above.
R5 and R6, R6 and R7, and R7 and R8 each may be linked to each other to form a ring. Examples of the compound in which R5 and R6 are linked to form a ring include 2-cyclohexylidenemethyl propionate, and 2-cyclopentylidenemethyl propionate. Examples of the compound in which R6 and R7 are linked to form a ring include methyl 1-cyclohexene-1-carboxylate, and methyl 1-cyclopentene-1-carboxylate. Examples of the compound in which R7 and R8 are linked to form a ring include α-methylene-δ-valerolactone, and α-methylene-γ-butyrolactone.
Among compounds that satisfy the conditions described above, the component A2 is preferably methyl acrylate, butyl acrylate, ethyl methacrylate, methyl crotonate, methyl cis-crotonate, isobutyl methacrylate, butyl methacrylate, propyl methacrylate, isopentyl methacrylate, methyl 2-methylene-3-butenoate, methyl 3,3-dimethylacrylate, methyl 2-ethylacrylate, methyl 2-pentenoate, methyl cinnamate, methyl 3-methoxyacrylate, dimethyl fumarate, methyl 2-cyclohexylidenepropionate, methyl 2-cyclopentylidenepropionate, methyl 1-cyclohexene-1-carboxylate, methyl 1-cyclopentene-1-carboxylate, α-methylene-δ-valerolactone, or α-methylene-γ-butyrolactone, more preferably methyl acrylate, butyl acrylate, ethyl methacrylate, methyl crotonate, methyl cis-crotonate, isobutyl methacrylate, butyl methacrylate, propyl methacrylate, isopentyl methacrylate, methyl 2-methylene-3-butenoate, methyl 3,3-dimethylacrylate, methyl 2-ethylacrylate, methyl 2-pentenoate, methyl cinnamate, methyl 3-methoxyacrylate, dimethyl fumarate, or methyl 1-cyclohexene-1-carboxylate, and still more preferably methyl acrylate, ethyl methacrylate, or methyl crotonate from the viewpoint of quality stability of methyl methacrylate-containing composition during storage.
One or two or more component(s) A2 may be contained in the methyl methacrylate-containing composition in the second aspect according to the present invention.
In preferred embodiments where the methyl methacrylate-containing composition comprises a component B, the component B is the same as the first aspect. One or two or more component(s) B may be contained.
In cases where the methyl methacrylate-containing composition comprises a compound that corresponds to both components A2 and B, the compound is considered as the component A2. Thus, the case where the methyl methacrylate-containing composition comprises the component A2 and the component B means that the composition comprises the component B other than the compound. In cases where two or more compounds that correspond to both components A2 and B are contained, the compound with the highest molar concentration in the methyl methacrylate composition is considered as the component A2, and the other compound(s) is/are considered as the component(s) B.
MB/MA2 is preferably 0.1 or more from the viewpoint of efficiency in reducing the production of methyl pyruvate. The upper limit of MB/MA2 is not particularly limited, and is usually 100 or less.
MA2 is from 1 to 40,000 μmol/L. When MA2 is 1 μmol/L or more, the effect of reducing the production of methyl methacrylate dimer and methyl pyruvate can be sufficiently obtained. When MA2 is 40,000 μmol/L or less, the impurity content after production of methyl methacrylate polymer by polymerization of the methyl methacrylate-containing composition according to the present invention is reduced, so that adverse effects on physical properties of the polymer can be prevented. The lower limit of MA2 is more preferably 10 μmol/L or more, and still more preferably 50 μmol/L or more. The upper limit of MA2 is more preferably 10,000 μmol/L or less, still more preferably 5,000 μmol/L or less, and most preferably 500 μmol/L or less.
Preferred embodiments of MB are the same as the first aspect.
In preferred embodiments, the concentration of methyl methacrylate is the same as the first aspect.
In preferred embodiments, the component C is the same as the first aspect.
The method of confirming that the methyl methacrylate-containing composition contains a component A2, a component B, a component C, and water, and the method of measuring the concentrations of methyl methacrylate, a component A2, a component B, a component C, and water are the same as the first aspect.
A methyl methacrylate-containing composition in a third aspect according to the present invention comprises methyl methacrylate, and at least one compound(s) (component A3) selected from the group consisting of methyl acrylate, butyl acrylate, ethyl methacrylate, methyl crotonate, methyl cis-crotonate, isobutyl methacrylate, butyl methacrylate, propyl methacrylate, isopentyl methacrylate, methyl 2-methylene-3-butenoate, methyl 3,3-dimethylacrylate, methyl 2-ethylacrylate, methyl 2-pentenoate, methyl cinnamate, methyl 3-methoxyacrylate, dimethyl fumarate, methyl 1-cyclohexene-1-carboxylate, methacrylamide, acrylic acid, crotonic acid, cis-crotonic acid, 3,3-dimethylacrylic acid, 2-ethylacrylic acid, 2-methylene -3-butenoic acid, and trans-3-hexen-2-one, wherein the concentration of methyl methacrylate is from 99 to 99.99% by mass. When the concentration of the component A3 is MA3 (μmol/L), MA3 is from 1 to 40,000 μmol/L.
The methyl methacrylate-containing composition may also contain the component B, the component C, or water as long as the composition satisfies a concentration of methyl methacrylate of from 99 to 99.99% by mass. Each item will be described in detail.
The methyl methacrylate-containing composition in the third aspect according to the present invention comprises at least one compound(s) (component A3) selected from the group consisting of methyl acrylate, butyl acrylate, ethyl methacrylate, methyl crotonate, methyl cis-crotonate, isobutyl methacrylate, butyl methacrylate, propyl methacrylate, isopentyl methacrylate, methyl 2-methylene-3-butenoate, methyl 3,3-dimethylacrylate, methyl 2-ethylacrylate, methyl 2-pentenoate, methyl cinnamate, methyl 3-methoxyacrylate, dimethyl fumarate, methyl 1-cyclohexene-1-carboxylate, methacrylamide, acrylic acid, crotonic acid, cis-crotonic acid, 3,3-dimethylacrylic acid, 2-ethylacrylic acid, 2-methylene-3-butenoic acid, and trans-3-hexen-2-one. When the methyl methacrylate-containing composition comprises a component A3, the component A3 as a single molecule can absorb a high amount of ultraviolet light, the production of hydroxyl radicals can be sufficiently reduced. Thus, even in cases where a component B which traps produced hydroxyl radicals is not present, the production of methyl methacrylate dimers and methyl pyruvate can be reduced. However, the methyl methacrylate-containing composition preferably comprises the component B as described above from the viewpoint that the production of methyl methacrylate dimers and methyl pyruvate can be reduced more.
The molecular weight of the component A3 is preferably 200 or less. When the molecular weight is 200 or less, the number of conjugated double bonds per unit mass can be increased, so that the effect of the present invention can be obtained with less weight. The molecular weight of the component A3 is more preferably 150 or less, still more preferably 130 or less, and particularly preferably 110 or less.
The component A3 is preferably at least one selected from the group consisting of methyl acrylate, methyl crotonate, acrylic acid, and crotonic acid.
One or two or more component(s) A3 may be contained in the methyl methacrylate-containing composition in the third aspect according to the present invention.
In preferred embodiments where the methyl methacrylate-containing composition comprises a component B, the component B is the same as the first aspect. One or two or more component(s) B may be contained.
In cases where the methyl methacrylate-containing composition comprises a compound that corresponds to both components A3 and B, the compound is considered as the component A3. Thus, the case where the methyl methacrylate-containing composition comprises the component A3 and the component B means that the composition comprises the component B other than the compound. In cases where two or more compounds that correspond to both components A3 and B are contained, the compound with the highest molar concentration in the methyl methacrylate composition is considered as the component A3, and the other compound(s) is/are considered as a component(s) B.
MB/MA3 is preferably 0.1 or more from the viewpoint of efficiency in reducing the production of methyl pyruvate. The upper limit of MB/MA3 is not particularly limited, and is usually 100 or less.
MA3 is from 1 to 40,000 μmol/L. When MA3 is 1 μmol/L or more, the effect of reducing the production of methyl methacrylate dimer and methyl pyruvate can be sufficiently obtained. When MA2 is 40,000 μmol/L or less, the impurity content after production of methyl methacrylate polymer by polymerization of the methyl methacrylate-containing composition according to the present invention is reduced, so that adverse effects on physical properties of the polymer can be prevented. The lower limit of MA3 is more preferably 10 μmol/L or more, and still more preferably 50 μmol/L or more. The upper limit of MA3 is more preferably 10,000 μmol/L or less, still more preferably 5,000 μmol/L or less, and most preferably 500 μmol/L or less.
The preferred embodiments of MB is the same as the first aspect.
The preferred embodiments of the concentration of methyl methacrylate is the same as the first aspect.
The preferred embodiments of the component C is the same as the first aspect.
The method of confirming that the methyl methacrylate-containing composition contains a component A3, a component B, a component C, and water, and the method of measuring the concentrations of methyl methacrylate, a component A3, a component B, a component C, and water are the same as the first aspect.
The method of producing the methyl methacrylate-containing composition according to the present invention may be a method in which a component A1, a component A2, or a component A3 (hereinafter correctively referred to as “component A”) and a component B are added to methyl methacrylate. Methyl methacrylate to be used may be a commercially available product, or methyl methacrylate produced by known methods such as the acetone cyanohydrin (ACH) method, the new acetone cyanohydrin (new ACH) method, the C4 direct oxidation method, the direct methyl esterification method, the ethylene method, and the new ethylene method may be used. The component A and the component B to be used may be commercially available products, or those synthesized by known methods may be used. When methyl methacrylate produced by a known method such as the acetone cyanohydrin (ACH) method, the new acetone cyanohydrin (new ACH) method, the C4 direct oxidation method, the direct methyl esterification method, the ethylene method, or the new ethylene method is used, the component A or the component B may be added to raw materials or in the course of the production process to produce the methyl methacrylate-containing composition. In cases where a component A or a component B is produced as a by-product during the methyl methacrylate production process, a part of the component A or the component B produced may be left for production of the methyl methacrylate-containing composition.
The methyl methacrylate-containing composition according to the present invention has high quality stability during storage. The method of evaluating the quality stability of the methyl methacrylate-containing composition during storage may be, for example, a method in which the methyl methacrylate-containing composition is actually stored for a long period, and the amounts of methyl methacrylate dimers and methyl pyruvate produced are determined. From the viewpoint of work simplicity, a method may be carried out in which the methyl methacrylate-containing composition is heated for a short time, and the amounts of methyl methacrylate dimers and methyl pyruvate produced are determined. In cases of heating for short time, the heating temperature is preferably from 50 to 100° C., and the heating time period is preferably from 1 to 24 hours. In the present invention, the quality stability of the methyl methacrylate-containing composition during storage is evaluated based on the amounts of methyl methacrylate dimers and methyl pyruvate produced when the methyl methacrylate-containing composition is stored at 25° C. for 14 days.
The method of producing methyl methacrylate polymer according to the present invention comprises a step of polymerizing a polymeric composition comprising the methyl methacrylate-containing composition according to the present invention.
The polymeric composition may comprise, as needed, a monomer that can be copolymerized with methyl methacrylate, and other additives.
Examples of the monomer that can be copolymerized with methyl methacrylate include the following:
a methacrylate ester, such as ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, or benzyl methacrylate;
an acrylate ester, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, or 2-ethylhexyl acrylate;
an unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, maleic acid, or itaconic acid;
an unsaturated carboxylic anhydride, such as maleic anhydride, or itaconic anhydride;
maleimide, such as N-phenylmaleimide, or N-cyclohexylmaleimide;
a vinyl monomer containing a hydroxy group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or 2-hydroxypropyl methacrylate;
a vinyl ester, such as vinyl acetate, or vinyl benzoate;
vinyl chloride, vinylidene chloride, and derivatives thereof;
a vinyl monomer containing nitrogen, such as methacrylamide, or acrylonitrile;
a monomer containing an epoxy group, such as glycidyl acrylate, or glycidyl methacrylate;
an aromatic vinyl monomer, such as styrene, or alpha-methylstyrene;
alkane diol di(meth)acrylate, such as ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butyleneglycol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate;
polyoxyalkylene glycol di(meth)acrylate, such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, or neopentyl glycol di(meth)acrylate;
a vinyl monomer having two or more ethylenic unsaturated bonds in its molecule, such as divinylbenzene;
an unsaturated polyester prepolymer obtained from at least one polyvalent carboxylic acid including ethylenic unsaturated polycarboxylic acid and at least one diol; and
a vinyl ester prepolymer obtained by acrylic modification of an end of an epoxy group.
Among those described above, the monomer that can be copolymerized with methyl methacrylate is preferably at least one selected from the group consisting of the methacrylate esters and the acrylate esters. This enables polymerization of the polymeric composition to obtain a methyl methacrylate polymer with excellent balance of transparency, heat resistance, and moldability. The monomer that can be copolymerized with methyl methacrylate is more preferably an acrylate ester, and particularly preferably at least one selected from the group consisting of methyl acrylate, ethyl acrylate, and n-butyl acrylate.
One or two or more monomer(s) that can be copolymerized with methyl methacrylate may be used. When the component A is a monomer that can be copolymerized with methyl methacrylate, the component A may be used as a monomer that can be copolymerized with methyl methacrylate, or a monomer that can be copolymerized with methyl methacrylate apart from the component A may be used.
The lower limit of the amount of the monomer that can be copolymerized with methyl methacrylate contained in the polymeric composition is preferably 0.01 parts by mass or more with respect to 100 parts by mass of methyl methacrylate. This enables obtaining a methyl methacrylate polymer with high transparency. The upper limit of the amount of the monomer that can be copolymerized with methyl methacrylate with respect to 100 parts by mass of methyl methacrylate is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less. The lower limit of the amount of the monomer that can be copolymerized with methyl methacrylate with respect to 100 parts by mass of methyl methacrylate is more preferably 0.1 parts by mass or more, and still more preferably 1 part by mass or more.
Other additives preferably include a polymerization initiator. Other additives may also include, for example, a chain transfer agent, a mold release agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant promoter, a polymerization inhibitor, a filler, a pigment, a dye, a silane coupling agent, a leveling agent, an antifoam, and a fluorescent agent, as needed. One or two or more other additive(s) may be contained.
Examples of the polymerization initiator include the following:
an azo compound, such as 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;
an organic peroxide, such as benzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-3,5,5-trimethyl hexanoate, t-butyl peroxylaurate, t-butyl peroxyacetate, t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy-2-ethyl hexanoate, t-amyl peroxy-2-ethyl hexanoate, 1,1,3,3-tetramethyl butyl peroxyethyl hexanoate, 1,1,2-trimethyl propyl peroxy-2-ethyl hexanoate, 1,1,3,3-tetramethyl butyl peroxyisopropyl monocarbonate, 1,1,2-trimethyl propyl peroxyisopropyl monocarbonate, 1,1,3,3-tetramethyl butyl peroxyisononanoate, 1,1,2-trimethyl propyl peroxy-isononanoate, di-t-butyl peroxide, di-t-hexyl peroxide, lauroyl peroxide, and dilauroyl peroxide;
a persulfate compound, such as potassium persulfate; and
a redox polymerization initiator.
Among those described above, the polymerization initiator is preferably at least one selected from the group consisting of the azo compound and the organic peroxide from the viewpoint of storage stability and reactivity with methyl methacrylate.
The amount of the polymerization initiator used is preferably from 0.0001 to 1 part by mass with respect to 100 parts by mass of the total of methyl methacrylate and the monomer that can be copolymerized with methyl methacrylate.
Examples of the polymerization method include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. From the viewpoints of environmental load due to the use of solvents and the like, and of transparency of the methyl methacrylate polymer to be obtained, a bulk polymerization method is preferable.
Specific means for the bulk polymerization method is not particularly limited, and a known casting polymerization method such as a cell casting method or a continuous casting method can be used for production.
The casting polymerization method is a method for obtaining methyl methacrylate polymer by injecting a polymeric composition into a mold composed of two inorganic glass plates or metal plates (for example, SUS plates) placed opposite each other at a predetermined distance with the periphery sealed with a gasket such as a soft resin tube, and allowing the composition to polymerize.
The mold for casting polymerization is not particularly limited, and known molds can be used. Examples of the mold for cell casting include those in which two plate-like bodies, such as inorganic glass plates, chromium-plated metal plates, and stainless steel plates, are placed opposite each other at a predetermined distance, and a gasket is placed around the periphery to allow the plate-like bodies and the gasket to form a sealed space. Examples of the mold for continuous casting include those in which a sealed space is formed by opposing faces of a pair of endless belts running in the same direction at the same speed, and gaskets running at the same speed as the endless belt on both sides of the endless belt.
The spacing of the void in a mold is adjusted as appropriate to obtain a resin sheet with a desired thickness, and is generally from 1 to 30 mm.
The polymerization temperature is preferably from 125 to 210° C. This enables achieving an appropriate polymerization rate. More preferably, the lower limit of the polymerization temperature is 130° C. or more, and the upper limit is 180° C. or less. The polymerization time is not particularly limited, and can be, for example, from 0.5 to 24 hours.
The present invention will be described in detail with reference to Examples and Comparative Examples below, but is not limited to these Examples. Unless otherwise stated, the terms “%” and “ppm” in the examples and the comparative examples mean “% by weight” and “ppm by weight,” respectively.
The water concentration contained in a methyl methacrylate reagent was determined by the Karl-Fischer method. The composition of the components of the methyl methacrylate-containing composition before being stored was determined based on the amounts of the raw materials added. Methyl methacrylate dimers and methyl pyruvate in the methyl methacrylate-containing composition after being stored were determined by an absolute calibration curve method using GC-MS. The measurement conditions for GC-MS are shown below.
Instrument: GC-MS measuring system (product name: QP-2010SE, manufactured by Shimadzu Corporation)
Column (product name: DB-WAX, manufactured by Agilent Technologies, Inc.);
Injection volume: 1.0 μL;
Vaporizing chamber temperature: 210° C.;
Column oven temperature: held at 35° C. for 10 minutes, raised from 35° C. to 150° C. at 5° C./min, held at 150° C. for 17 minutes, raised from 150° C. to 220° C. at 5° C./min, and held at 220° C. for 6 minutes;
Carrier gas: helium;
Injection mode: split (split ratio: 50);
Control mode: constant linear velocity (25.0 cm/sec);
Pressure: 26.1 KPa;
Total flow: 52.5 mL/min;
Purge flow: 3.0 mL/min; and
Column flow: 0.97 mL/min.
Ionization method: EI (Electron Ionization);
Ion source temperature: 250° C.;
Interface temperature: 250° C.;
m/z detection range: 10 to 300; and
Detection time: 70 minutes.
Determination of the water concentration by the Karl-Fischer method was carried out using automated water measurement equipment (product name: AQV-2200, manufactured by Hiranuma Co., Ltd.).
Using methyl acrylate as a component A, 0.0186 g of the component A was added to 10.0701 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate solution (A-1 solution). The concentration of the component A in the A-1 solution is shown in Table 1.
Using 2,4-dimethyl-6-t-butylphenol as a component B, 0.0228 g of the component B was added to 10.0026 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate solution (B-1 solution). The concentration of the component B in the B-1 solution is shown in Table 1.
Next, 0.1072 g of the A-1 solution and 0.1062 g of the B-1 solution were added to 20.0348 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate-containing composition. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2. The concentration of the component A in the methyl methacrylate-containing composition is defined as MA (μmol/L).
The obtained methyl methacrylate-containing composition was stored at 25° C. for 14 days. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
A-1 solutions were prepared in the same manner as in Example 1 except that a compound shown in Table 1 was used as a component A, and the amounts of the methyl methacrylate reagent and the component A were changed as shown in Table 1.
B-1 solutions were prepared in the same manner as in Example 1.
Next, methyl methacrylate-containing compositions were prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent, the A-1 solution, and the B-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing compositions were stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing compositions after the storage are shown in Table 2.
A-1 solutions were prepared in the same manner as in Example 1 except that a compound shown in Table 1 was used as a component A, and the amounts of the methyl methacrylate reagent and the component A were changed as shown in Table 1.
B-1 solutions were prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent and the component B were changed as shown in Table 1.
Next, methyl methacrylate-containing compositions were prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent, the A-1 solution, and the B-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing compositions are shown in Table 2.
The obtained methyl methacrylate-containing compositions were stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing compositions after the storage are shown in Table 2.
A-1 solutions were prepared in the same manner as in Example 1.
B-1 solutions were prepared in the same manner as in Example 1 except that a compound shown in Table 1 was used as a component B, and the amounts of the methyl methacrylate reagent and the component B were changed as shown Table 1.
Next, methyl methacrylate-containing compositions were prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent, the A-1 solution, and the B-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing compositions are shown in Table 2.
The obtained methyl methacrylate-containing compositions were stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing compositions after the storage are shown in Table 2.
An A-1 solution and a B-1 solution were prepared in the same manner as in Example 1.
Next, a methyl methacrylate-containing composition was prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent, the A-1 solution, and the B-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
A B-1 solution was prepared in the same manner as in Example 1.
Next, using methyl acrylate as a component A, 0.0205 g of a component A and 0.1086 g of a B-1 solution were added to 20.0166 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate-containing composition. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
A B-1 solution was prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent and the component B were changed as shown in Table 1.
Next, a methyl methacrylate-containing composition was prepared in the same manner as in Example 24 except that the amounts of the methyl methacrylate reagent, the component A, and the B-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
An A-1 solution and a B-1 solution were prepared in the same manner as in Example 1.
Next, a methyl methacrylate-containing composition was prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent, the A-1 solution, and the B-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
A-1 solutions were prepared in the same manner as in Example 1.
B-1 solutions were prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent and the component B were changed as shown in Table 1.
Next, methyl methacrylate-containing compositions were prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent, the A-1 solution, and the B-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing compositions are shown in Table 2.
The obtained methyl methacrylate-containing compositions were stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing compositions after the storage are shown in Table 2.
An A-1 solution was prepared in the same manner as in Example 1.
Next, 0.1048 g of the A-1 solution was added to 20.0196 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate-containing composition. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
A B-1 solution was prepared in the same manner as in Example 1.
Next, 0.2213 g of the B-1 solution was added to 40.0273 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate-containing composition. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
40.0000 g of a methyl methacrylate reagent (water concentration: 240 ppm) was used as a methyl methacrylate-containing composition and stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
A B-1 solution was prepared in the same manner as in Example 1.
Using diacetyl as a component C, 0.0205 g of the component C was added to 9.9913 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate solution (C-1 solution). The concentration of the component C in the C-1 solution is shown in Table 1.
Next, 0.2151 g of the B-1 solution and 0.2069 g of the C-1 solution were added to 40.0218 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate-containing composition. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
An A-1 solution was prepared in the same manner as in Example 1 except that a compound shown in Table 1 was used as a component A, and the amounts of the methyl methacrylate reagent and the component A were changed as shown in Table 1.
Next, a methyl methacrylate-containing composition was prepared in the same manner as in Example 29 except that the amounts of the methyl methacrylate reagent and the A-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
A B-1 solution was prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent and the component B were changed as shown in Table 1.
Next, a methyl methacrylate-containing composition was prepared in the same manner as in Example 24 except that the amounts of the methyl methacrylate reagent, the component A, and the B-1 solution were changed as shown in Table 2. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
An A-1 solution was prepared in the same manner as in Example 1.
A B-1 solution was prepared in the same manner as in Example 1 except that the amounts of the methyl methacrylate reagent and the component B were changed as shown in Table 1.
Next, 0.1106 g of the A-1 solution, 0.0993 g of the B-1 solution, and 0.2937 g of pure water were added to 20.0064 g of a methyl methacrylate reagent (water concentration: 240 ppm) to prepare a methyl methacrylate-containing composition. The concentrations of the components in the methyl methacrylate-containing composition are shown in Table 2.
The obtained methyl methacrylate-containing composition was stored as in Example 1. The amounts of methyl methacrylate dimers and methyl pyruvate produced in the methyl methacrylate-containing composition after the storage are shown in Table 2.
5
4
03
158
09
indicates data missing or illegible when filed
As shown in Tables 1 and 2, Examples 1 to 28 in which the methyl methacrylate-containing composition contains defined components A and B show reduction of both production of methyl methacrylate dimers and methyl pyruvate in the methyl methacrylate compositions after storage, and can be said to have high quality stability during storage. Example 29 containing defined concentrations of components corresponding to the components A2 and A3 show reduction of both production of methyl methacrylate dimers and methyl pyruvate in the methyl methacrylate composition after storage even without a component B, and can be said to have high quality stability during storage.
The polymeric composition comprising each methyl methacrylate-containing composition obtained in each Example can be polymerized to obtain a methyl methacrylate polymer.
According to the present invention, methyl methacrylate-containing compositions that can be used, for example, as raw materials for acrylic resins can be stored stably for a long period of time, which is industrially useful.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-075626 | Apr 2021 | JP | national |
This application is a Continuation of PCT International Application No. PCT/JP2022/019004, filed on Apr. 27, 2022, which is claiming priority of Japanese Patent Application No. 2021-075626, filed on Apr. 28, 2021, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2022/019004 | Apr 2022 | US |
| Child | 18383440 | US |
