Methacrylate-containing compositions and methods of making methacrylate polymers

Abstract

An object of the present application is to provide a methyl methacrylate-containing composition with high quality stability during storage. The object is solved by a methyl methacrylate-containing composition comprising methyl methacrylate, a nitrile compound represented by the following formula (1), and a polymerization inhibitor, and the concentration of methyl methacrylate is 99 to 99.99 mass%.

Description

Technical Field

[0001] This invention relates to compositions containing methyl methacrylate and methods for manufacturing methyl methacrylate polymers. Background Technology

[0002] Methyl methacrylate (hereinafter also referred to as "MMA") is a known extremely useful substance that can be used as a raw material for various applications and polymers. For example, polymethyl methacrylate (PMMA), a homopolymer of PMMA, is used in signage, lighting equipment, automotive parts, building materials, light guide plates for flat panel displays, and light diffusion plates due to its excellent transparency and weather resistance. Furthermore, copolymers of PMMA with other monomers are used in coatings, adhesives, resin modifiers, artificial marble, and paper coating latex. Various industrial manufacturing methods for PMMA have been developed, including the acetone cyanohydrin (ACH) method, the modified acetone cyanohydrin (new ACH) method, the C4 direct oxidation method, the direct methylation method, the ethylene method, and the modified ethylene method (Non-Patent Literature 1). In these manufacturing methods, unreacted raw materials and byproducts contained in the generated PMMA are removed through purification processes such as distillation to obtain PMMA of suitable quality for the target application.

[0003] It is known that methyl methacrylate (MMA) readily polymerizes; therefore, polymerization inhibitors are added during the manufacture and storage of MMA to maintain its quality (Non-Patent Document 2). For example, Patent Document 1 describes hydroquinone methyl ether (MEHQ) as a particularly preferred polymerization inhibitor. Patent Document 2 describes N,N'-dialkyl-p-phenylenediamine and nitroxide radicals as preferred polymerization inhibitors. Patent Document 3 describes distilling MMA in the presence of a phenolic polymerization inhibitor. Patent Document 4 describes the use of diphenylamine derivatives as polymerization inhibitors. Patent Document 5 describes the use of phenyltriamine derivatives as polymerization inhibitors.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2004-155757

[0007] Patent Document 2: Japanese Patent Publication No. 2005-502695

[0008] Patent Document 3: Japanese Patent Publication No. 10-504553

[0009] Patent Document 4: Japanese Patent Publication No. 2002-533309

[0010] Patent Document 5: Japanese Patent Publication No. 2002-513034

[0011] Non-patent literature

[0012] Non-Patent Literature 1: Toru Kuroda, “Development of Catalysts for the Production of Methyl Methacrylate”, Catalyst, Catalyst Research Society, 2003, Vol. 45, No. 5, pp. 366-371

[0013] Non-Patent Literature 2: Takayuki Otsu, “Function of Polymerization Inhibitors”, Organic Synthetic Chemistry, Organic Synthetic Chemistry Association, 1975, Vol. 33, No. 8, pp. 634-640 Summary of the Invention

[0014] However, even with the addition of the aforementioned polymerization inhibitors, methyl methacrylate sometimes deteriorates in quality during storage. Based on this, the object of the present invention is to provide a methyl methacrylate-containing composition with high quality stability during storage.

[0015] The inventors conducted in-depth research to achieve the aforementioned objectives. As a result, they discovered that in methyl methacrylate (MMA) whose quality deteriorates during storage, the concentration of MMA decreases, leading to the formation of MMA dimers and methyl pyruvate. If MMA contains MMA dimers, structural changes in the resulting MMA polymer may occur, adversely affecting its physical properties. Furthermore, if MMA contains methyl pyruvate, it can cause discoloration in the resulting MMA polymer. Therefore, by including a nitrile compound with a specific structural formula in the composition containing MMA, the quality stability during storage is improved, and the formation of MMA dimers and methyl pyruvate is suppressed, thus completing this invention.

[0016] That is, the present invention is as follows [1] to

[16] .

[0017] [1]: A composition of methyl methacrylate comprising: methyl methacrylate, a nitrile compound represented by the following formula (1) (component A), and a polymerization inhibitor (component B),

[0018] The concentration of methyl methacrylate is 99–99.99% by mass.

[0019] RC≡N (1)

[0020] (In the above formula (1), R represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. These groups may further have substituents.)

[0021] [2]: The composition containing methyl methacrylate according to [1], wherein when the concentration of the above-mentioned component A is set to MA (μmol / L) and the concentration of the above-mentioned component B is set to MB (μmol / L), MB / MA is 0.003 or more.

[0022] [3]: The composition containing methyl methacrylate according to [1] or [2], wherein when the concentration of the above component A is set as MA (μmol / L), MA is 1 to 20000 μmol / L.

[0023] [4]: The composition containing methyl methacrylate according to [3], wherein the above-mentioned MA is 10 to 15000 μmol / L.

[0024] [5]: The composition containing methyl methacrylate according to any one of [1] to [4], wherein when the concentration of the above component B is set to MB (μmol / L), MB is 1 to 5000 μmol / L.

[0025] [6]: The composition containing methyl methacrylate according to [5], wherein the MB is 10 to 2500 μmol / L.

[0026] [7]: The composition containing methyl methacrylate according to any one of [1] to [6], wherein the molecular weight of the above-mentioned component A is 1000 or less.

[0027] [8]: A composition containing methyl methacrylate according to any one of [1] to [7], wherein the above-mentioned component B is at least one polymerization inhibitor selected from phenolic compounds, quinone compounds, nitrobenzene compounds, nitroso radical compounds, amine compounds, phosphorus-containing compounds, sulfur-containing compounds, iron-containing compounds, copper-containing compounds and manganese-containing compounds.

[0028] [9]: The composition containing methyl methacrylate according to any one of [1] to [8], wherein component B is at least one polymerization inhibitor selected from phenolic compounds, nitroxide radical compounds, amine compounds, phosphorus-containing compounds and sulfur-containing compounds.

[0029]

[10] : The composition containing methyl methacrylate according to any one of [1] to [9], wherein the above-mentioned component B is at least one polymerization inhibitor selected from hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, N,N-diphenylamine, N-nitrosodiphenylamine, triphenyl phosphite and phenothiazine.

[0030]

[11] : The composition containing methyl methacrylate according to any one of [1] to

[10] , wherein the concentration of methyl methacrylate is 99.8 to 99.99% by mass.

[0031]

[12] : The composition containing methyl methacrylate according to any one of [1] to

[11] , wherein it does not contain diacetyl or the concentration of diacetyl contained therein is less than 55 μmol / L.

[0032]

[13] : A composition containing methyl methacrylate according to any one of [1] to

[12] , wherein, in the above formula (1), R is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or an aryl group having 6 to 8 carbon atoms.

[0033]

[14] : A composition containing methyl methacrylate according to any one of [1] to

[13] , wherein R in the above formula (1) is methyl, ethyl, vinyl, isopropyl or phenyl.

[0034]

[15] : A method for manufacturing a methyl methacrylate polymer, comprising the following steps: polymerizing a polymerizable composition comprising any one of the compositions containing methyl methacrylate described in [1] to

[14] .

[0035]

[16] : The method for manufacturing methyl methacrylate polymer according to

[15] , wherein the polymerizable composition comprises a monomer that can be copolymerized with methyl methacrylate.

[0036] According to the present invention, a methyl methacrylate-containing composition with high quality stability can be provided, in which the formation of methyl methacrylate dimer and methyl pyruvate during storage is suppressed. Detailed Implementation

[0037] The embodiments of the present invention will be described below, but the present invention is not limited to the following.

[0038] In this specification, the numerical range represented by “~” indicates the range of values ​​recorded before and after “~” as the lower and upper limits. “A~B” means above A and below B.

[0039] [Compositions containing methyl methacrylate]

[0040] The composition containing methyl methacrylate of the present invention comprises methyl methacrylate, a nitrile compound represented by the following formula (1) (component A) and a polymerization inhibitor (component B), wherein the concentration of methyl methacrylate is 99 to 99.99% by mass.

[0041] R—CN(1)

[0042] In the above formula (1), R represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. These groups may further have substituents.

[0043] In addition, this composition containing methyl methacrylate may also contain other compounds (component C) and water, provided that the concentration of methyl methacrylate is 99-99.99% by mass. Detailed descriptions of each item are provided below.

[0044] (ingredient A)

[0045] The methyl methacrylate-containing composition of the present invention comprises a nitrile compound (component A) represented by formula (1) above. By including component A in the methyl methacrylate-containing composition, the formation of methyl methacrylate dimer and methyl pyruvate during storage of the methyl methacrylate-containing composition can be suppressed. The reason for this is as follows.

[0046] Component B, described later, inhibits the dimerization reaction of methyl methacrylate (MMA) based on a free radical mechanism by capturing free radicals generated in MMA. However, the dimerization reaction of MMA also proceeds based on a cationic mechanism in the presence of an acid catalyst. Since nitrile compound A is weakly basic, it is believed that it can inhibit the dimerization reaction of MMA by capturing trace amounts of acidic substances present in the MMA composition and suppressing their function as an acid catalyst. Therefore, it is considered that since components A and B inhibit the MMA dimerization reaction through different mechanisms, the coexistence of both can efficiently inhibit the formation of MMA dimers. Furthermore, MMA hydrolyzes under alkaline conditions, but nitrile compounds are weakly basic and do not possess the strong basicity to cause the hydrolysis of MMA. Therefore, component A is effective as a basic substance that captures trace amounts of acidic substances.

[0047] On the other hand, methyl methacrylate is oxidized by hydroxyl radicals and oxygen molecules to produce methyl pyruvate. Component B can capture hydroxyl radicals, while component A can capture the radical intermediate generated by the reaction of hydroxyl radicals with methyl methacrylate, and the intermediate is returned to methyl methacrylate. Therefore, it is believed that the coexistence of components A and B can efficiently inhibit the formation of methyl pyruvate.

[0048] The molecular weight of component A is preferably 1000 or less. By making the molecular weight 1000 or less, the number of cyano groups per unit mass in component A can be increased, thus achieving the effects of the present invention with a smaller mass. The molecular weight of component A is more preferably 800 or less, further preferably 600 or less, and particularly preferably 400 or less.

[0049] In the above formula (1), R represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. These groups may further have substituents.

[0050] When R meets the above conditions, the weak basicity of component A and its reactivity with acidic substances and free radicals can be maintained, thus achieving the effects of the present invention. Furthermore, since it is a highly stable group, it can prevent component A from transforming into other compounds during storage. R is preferably an alkyl group with 1 to 3 carbon atoms, an alkenyl group with 2 to 3 carbon atoms, or an aryl group with 6 to 8 carbon atoms. R is more preferably methyl, ethyl, vinyl, isopropenyl, or phenyl.

[0051] The alkyl group is a chain (straight-chain or branched) alkyl group or a cyclic alkyl group. Examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and isopentyl. Among these, methyl, ethyl, n-propyl, and isopropyl are preferred, and methyl or ethyl are more preferred. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, and cyclopentyl.

[0052] The alkenyl group can be a chain (straight-chain or branched) alkenyl or a cyclic alkenyl. Examples of chain alkenyl groups include vinyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, and 2-pentenyl. Among these, vinyl, 1-propenyl, and isopropenyl are preferred, and vinyl or isopropenyl are more preferred. Examples of cyclic alkenyl groups include cyclopropenyl, cyclobutenyl, and cyclopentenyl.

[0053] Aryl groups include heteroaryl groups containing oxygen, nitrogen, sulfur, etc. Examples of aryl groups include phenyl, mesitylene, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, and isophenyl. Azolyl, isothiazolyl, imidazole, Azolyl, thiazolyl, thiadiazolyl, thiophene, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrrolyl, furanyl, furazanyl, isoquinolinyl, isoindolyl, indolyl, quinolinyl, pyridothiazolyl, benzimidazolyl, benzo[] Azolyl, benzothiazolyl, benzotriazolyl, benzofuranyl, imidazopyridyl, triazolpyridyl, purine, etc.

[0054] When R is an alkyl, alkenyl, or aryl group with a substituent, examples of substituents include alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, a monovalent group containing a carbonyl group, alkylthio, and arylthio. Among these, hydroxyl, alkoxy, amino, a monovalent group containing a carbonyl group, and alkylthio are preferred, and hydroxyl, methoxy, amino, acetyl, and methylthio are more preferred. The molecular weight of the substituent is preferably 200 or less, more preferably 100 or less, and even more preferably 50 or less. It should be noted that the number of carbon atoms in R refers to the number of carbon atoms in the substituents contained in the alkyl, alkenyl, or aryl group. For example, R in 4-(methylthio)benzonitrile is 4-(methylthio)phenyl, which is considered to be an aryl group having 7 carbon atoms.

[0055] The alkyl group used as a substituent is the same as the alkyl group described above, as long as R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. The alkyl group used as a substituent has 1 to 11 carbon atoms, preferably 1 to 6, and more preferably 1 to 3.

[0056] The alkenyl group used as a substituent is the same as the alkenyl group described above, as long as R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. The alkenyl group used as a substituent has 2 to 11 carbon atoms, preferably 2 to 6, and more preferably 2 to 3.

[0057] The aryl group used as a substituent is the same as the aryl group described above, as long as R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. The aryl group used as a substituent has 1 to 11 carbon atoms, preferably 3 to 9, and more preferably 5 to 7.

[0058] The alkoxy group that serves as a substituent is an alkoxy group with 1 to 11 carbon atoms, preferably an alkoxy group with 1 to 6 carbon atoms, and more preferably an alkoxy group with 1 to 3 carbon atoms. R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, and phenoxy.

[0059] The substituent amino group includes an amino group (-NH2) without a substituent on the nitrogen atom, and an amino group in which some or all of the hydrogen atoms bonded to the nitrogen atom are replaced by carbon atoms. The number of carbon atoms in the amino group that is replaced by carbon atoms is 1 to 11, preferably 1 to 6, more preferably 1 to 3. R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. Examples of amino groups include methylamino, ethylamino, propylamino, butylamino, dimethylamino, diethylamino, aniline, toluidine, anisidine, N-methyl-N-phenylamino, etc.

[0060] Examples of monovalent groups containing carbonyl groups that can be used as substituents include formyl, acyl, carboxyl, amide, alkoxycarbonyl, thiocarboxyl, and thioester groups.

[0061] The acyl group is a substituent formed by linking a carbonyl group to an alkyl, alkenyl, or aryl group. The total number of carbon atoms from the carbonyl group (1) and the acyl group from the alkyl, alkenyl, or aryl group is 2 to 11, preferably 2 to 7, and more preferably 2 to 4. R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. Examples of acyl groups include acetyl, propionyl, butylcarbonyl, vinylcarbonyl, and benzoyl.

[0062] The amide group includes an unsubstituted amide group (-CONH2) on the nitrogen atom, and an amide group in which some or all of the hydrogen atoms bonded to the nitrogen atom are replaced by carbon atoms. The number of carbon atoms in the amide group is 1 to 11, preferably 1 to 7, and more preferably 1 to 4, totaling the number of carbon atoms from the carbonyl group (1) and the number of carbon atoms substituted on the nitrogen atom. R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. Examples of amide groups include unsubstituted amide groups, N-methylamido, N-ethylamido, N-phenylamido, N,N-dimethylamido, and N-methyl-N-phenylamido.

[0063] An alkoxycarbonyl group is a substituent formed by linking a carbonyl group to an alkoxy group, and is also called an ester group. The total number of carbon atoms from the carbonyl group (1) and the number of carbon atoms from the alkoxy group is 2 to 11, preferably 2 to 7, and more preferably 2 to 4. R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. Examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl.

[0064] The thioester group is a substituent formed by linking a carbonyl group to an alkylthio group or an arylthio group. The total number of carbon atoms from the carbonyl group (1) and the number of carbon atoms from the alkylthio group or the arylthio group is 2 to 11, preferably 2 to 7, and more preferably 2 to 4. R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. Examples of thioester groups include methylthiocarbonyl, ethylthiocarbonyl, butylthiocarbonyl, and phenylthiocarbonyl.

[0065] Furthermore, as a monovalent group containing a carbonyl group, it can be a substituent in which one or more hydrogen atoms of an alkyl group are replaced with carbonyl groups. Examples of such substituents include 2-acetoxyethyl, 2-acetylethyl, and 2-(acetylacetoxy)ethyl.

[0066] The alkylthio group used as a substituent is an alkylthio group with 1 to 11 carbon atoms, preferably an alkylthio group with 1 to 6 carbon atoms, and more preferably an alkylthio group with 1 to 3 carbon atoms. R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. Examples of alkylthio groups include methylthio, ethylthio, propylthio, and isopropylthio.

[0067] The arylthio group used as a substituent is an arylthio group with 1 to 11 carbon atoms, preferably an arylthio group with 3 to 9 carbon atoms, and more preferably an arylthio group with 5 to 7 carbon atoms. R is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 1 to 12 carbon atoms. Examples of arylthio groups include phenylthio and toluenethio.

[0068] From the viewpoint of quality stability during the storage of compositions containing methyl methacrylate, component A is preferably methacrylonitrile, acetonitrile, propionitrile, acrylonitrile, benzonitrile, cyclohexanenitrile, 3-hydroxypropionitrile, 3-methoxypropionitrile, 2-hydroxypropionitrile, 2-aminopropionitrile, 4-cyanophenol, 4-aminobenzonitrile, 4'-cyanoacetophenone, or 4-(methylthio)benzonitrile, more preferably methacrylonitrile, acetonitrile, propionitrile, acrylonitrile, benzonitrile, 3-hydroxypropionitrile, 3-methoxypropionitrile, 4-aminobenzonitrile, 4'-cyanoacetophenone, or 4-(methylthio)benzonitrile, and even more preferably methacrylonitrile, acetonitrile, propionitrile, acrylonitrile, benzonitrile, 3-hydroxypropionitrile, or 4-(methylthio)benzonitrile, and even more preferably methacrylonitrile, acetonitrile, propionitrile, acrylonitrile, benzonitrile, 3-hydroxypropionitrile, or 4-(methylthio)benzonitrile.

[0069] Component A can be one or more.

[0070] (Ingredient B)

[0071] The composition containing methyl methacrylate of the present invention includes a polymerization inhibitor (component B). It should be noted that, in this specification, a polymerization inhibitor refers to a compound that functions to inhibit the polymerization reaction of methyl methacrylate. Examples of polymerization inhibitors 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. By including component B, the polymerization reaction of methyl methacrylate based on a free radical polymerization mechanism during the storage of methyl methacrylate can be inhibited. Furthermore, as mentioned above, the coexistence of components A and B can efficiently inhibit the formation of methyl methacrylate dimers and the formation of methyl pyruvate due to the oxidation of methyl methacrylate.

[0072] Examples of phenolic inhibitors include alkylphenols, hydroxyphenols, aminophenols, nitrophenols, nitrosophenols, alkoxyphenols, and tocopherols.

[0073] Examples of alkylphenols 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'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), and 3,5-di-tert-butyl-4-hydroxytoluene.

[0074] Examples of hydroxyphenols include hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-pentylhydroquinone, 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.

[0075] Examples of aminophenols include o-aminophenol, m-aminophenol, p-aminophenol, 2-(N,N-dimethylamino)phenol, and 4-(ethylamino)phenol.

[0076] Examples of nitrophenols include o-nitrophenol, m-nitrophenol, p-nitrophenol, and 2,4-dinitrophenol.

[0077] Examples of nitrosophenols include ortho-nitrosophenol, meta-nitrosophenol, p-nitrosophenol, and α-nitroso-β-naphthol.

[0078] Examples of alkoxyphenols include 2-methoxyphenol, 2-ethoxyphenol, 2-isopropoxyphenol, 2-tert-butoxyphenol, 4-methoxyphenol, 4-ethoxyphenol, 4-propoxyphenol, 4-butoxyphenol, 4-tert-butoxyphenol, 4-heptoxyphenol, hydroquinone monobenzyl ether, tert-butyl-4-methoxyphenol, di-tert-butyl-4-methoxyphenol, pyrogallol-1,2-dimethyl ether, and hydroquinone monobenzoate.

[0079] Examples of tocopherols include α-tocopherol and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran.

[0080] Examples of inhibitors for polymerization of quinone compounds 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.

[0081] Examples of inhibitors for the polymerization of nitrobenzene compounds include nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrobenzene, dinitrotoluene, and 2,2-diphenyl-1-picrylhydrazine.

[0082] Examples of polymerization inhibitors that act as inhibitors for nitroxide radical compounds include 4-hydroxy-2,2,6,6-tetramethyl-piperidine-nitroxide radical, 4-oxo-2,2,6,6-tetramethyl-piperidine-nitroxide radical, 4-acetoxy-2,2,6,6-tetramethyl-piperidine-nitroxide radical, 2,2,6,6-tetramethyl-piperidine-nitroxide radical, piperidine-1-oxy radical, 4-(dimethylamino)-2,2,6,6-tetramethyl-piperidine-nitroxide radical, 4-amino-2,2,6,6-tetramethyl-piperidine-nitroxide radical, 4-ethanoloxy-2,2,6,6-tetramethyl-piperidine-nitroxide radical, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-nitroxide radical. Free radicals, 2,2,5,5-tetramethyl-piperidine-nitrogenoxide radicals, 3-amino-2,2,5,5-tetramethyl-piperidine-nitrogenoxide radicals, 4,4',4”-tris(2,2,6,6-tetramethyl-piperidine-nitrogenoxide radicals) phosphite, 3-oxo-2,2,5,5-tetramethylpyrrolidine-nitrogenoxide radicals, pyrrolidine-1-oxo radicals, 2,2,5,5-tetramethyl-1-oxa-3-azacyclopentyl-3-oxo radicals, 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-dioxo radicals, di-tert-butylnitrooxy, di-tert-pentylnitrooxy, etc.

[0083] Examples of polymerization inhibitors for amine compounds include N,N-diphenylamine, alkylated diphenylamine, 4,4'-dicumyl diphenylamine, 4,4'-dioctyl diphenylamine, 4-amino diphenylamine, p-nitrosodiphenylamine, N-nitrosodinamine, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosophenylhydroxylamine, N,N'-dialkyl-p-phenylenediamine (alkyl groups may be the same or different, and each group is composed of 1 to 4 carbon atoms independently of each other, and may be linear or segmented), N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, and N,N'-di(2-naphthyl)-p-phenylamine. p-Phenylenediamine, N,N-diethylhydroxylamine, 1,4-phenylenediamine, N-(1,4-dimethylpentyl)-N'-phenyl-1,4-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, butyrolactone-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, etc.

[0084] Examples of phosphorus-containing compound polymerization inhibitors include triphenylphosphine, triphenyl phosphite, triethyl phosphite, tri(isodecyl) phosphite, tri(tetrazyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di(tetrazyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, phosphonate [1,1-diphenyl-4,4'-diyl-bis[tetra-2,4-bis(1,1-dimethylethyl)phenyl]] ester, triphenyl phosphite, tri(nonylphenyl) phosphite, 4,4'-isopropylidene diphenylalkyl phosphite, tri(2,4-di-tert-butylphenyl) phosphite, and triphosphite. Biphenyl ester, distearate pentaerythritol diphosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetra(tetrazyl)-4,4'-butylidene bis(3-methyl-6-tert-butylphenol) diphosphite, hexa(tetrazyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 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, 1,3-bis(diphenoxyphosphoryloxy)benzene, etc.

[0085] Examples of sulfur-containing compounds that can act as polymerization inhibitors 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)phenothiazine onium chloride, and elemental sulfur.

[0086] Examples of inhibitors for polymerization of iron-containing compounds include ferric chloride.

[0087] Examples of copper-containing compound polymerization inhibitors include copper dimethyl dithiocarbamate, copper diethyl dithiocarbamate, copper dibutyl dithiocarbamate, copper salicylate, copper acetate, copper thiocyanate, copper nitrate, copper chloride, copper carbonate, copper hydroxide, copper acrylate, and copper methacrylate.

[0088] Examples of manganese-containing compound polymerization inhibitors include manganese dialkyl dithiocarbamate (the alkyl group can be any one of methyl, ethyl, propyl, or butyl, and can be the same or different), manganese diphenyl dithiocarbamate, manganese formate, manganese acetate, manganese octanoate, manganese naphthenate, manganese permanganate, and manganese salts of ethylenediaminetetraacetic acid.

[0089] From the viewpoint of ensuring the quality stability of the composition containing methyl methacrylate during storage, component B is preferably at least one polymerization inhibitor selected from phenolic compounds, nitroxide radical compounds, amine compounds, phosphorus-containing compounds, and sulfur-containing compounds. More preferably, it is at least one polymerization inhibitor selected from hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, N,N-diphenylamine, N-nitrosodiphenylamine, triphenyl phosphite, and phenothiazine.

[0090] Component B can be one or more.

[0091] It should be noted that if a composition containing methyl methacrylate contains a compound that belongs to both component A and component B, that compound is considered component B. That is, a composition containing methyl methacrylate must contain component A, which is different from that compound. It should also be noted that if two or more compounds that belong to both component A and component B are contained, the compound with the highest molar concentration in the methyl methacrylate composition is considered component B, and all other compounds are considered component A.

[0092] (Concentrations of component A and component B)

[0093] When the concentration of component A is set to MA (μmol / L) and the concentration of component B is set to MB (μmol / L), from the viewpoint of efficiency in suppressing the formation of methyl methacrylate dimer and methyl pyruvate, MB / MA is preferably 0.003 or higher. Furthermore, there is no particular upper limit to MB / MA, which is typically 100 or lower, and preferably 50 or lower.

[0094] The concentration of MA is preferably 1 to 20,000 μmol / L. By setting MA to 1 μmol / L or higher, sufficient suppression of the formation of methyl methacrylate dimer and methyl pyruvate can be achieved. Furthermore, by setting MA to 20,000 μmol / L or lower, the amount of impurities when manufacturing methyl methacrylate polymers through polymerization of the composition containing methyl methacrylate of the present invention can be reduced, preventing adverse effects on the physical properties of the polymer. The lower limit of MA is more preferably 10 μmol / L or higher, further preferably 50 μmol / L or higher, and particularly preferably 60 μmol / L or higher. The upper limit of the concentration of component A is more preferably 15,000 μmol / L or lower, further preferably 10,000 μmol / L or lower, particularly preferably 5,000 μmol / L or lower, and most preferably 1,000 μmol / L or lower.

[0095] MB is preferably 1 to 5000 μmol / L. By setting MB to 1 μmol / L or higher, the formation of methyl methacrylate dimer and methyl pyruvate can be sufficiently suppressed. Furthermore, by setting MB to 5000 μmol / L or lower, the amount of impurities when manufacturing methyl methacrylate polymers through polymerization of the composition containing methyl methacrylate of the present invention can be reduced, preventing adverse effects on the physical properties of the polymer. The lower limit of MB is more preferably 10 μmol / L or higher, and even more preferably 30 μmol / L or higher. The upper limit of the concentration of component B is more preferably 2500 μmol / L or lower, even more preferably 2000 μmol / L or lower, particularly preferably 1000 μmol / L or lower, and most preferably 600 μmol / L or lower.

[0096] (Concentration of methyl methacrylate)

[0097] The concentration of methyl methacrylate in the composition containing methyl methacrylate of the present invention is 99 to 99.99% by mass. By making the concentration of methyl methacrylate 99% by mass or more, the amount of impurities when manufacturing methyl methacrylate polymers by polymerizing the composition containing methyl methacrylate of the present invention can be reduced, preventing adverse effects on the physical properties of the polymer. In addition, by making the concentration of methyl methacrylate 99.99% by mass or less, purification costs can be reduced. The lower limit of the concentration of methyl methacrylate is preferably 99.8% by mass or more.

[0098] (Ingredient C)

[0099] The methyl methacrylate-containing composition of the present invention may contain other compounds (component C) as long as the concentration of methyl methacrylate is 99 to 99.99% by mass. Examples of component C include impurities generated during the manufacturing process of methyl methacrylate. For example, diacetyl is sometimes present as an impurity in methyl methacrylate. From the viewpoint of reducing coloration in the methyl methacrylate-containing composition, the concentration of diacetyl is preferably 55 μmol / L or less, more preferably 20 μmol / L or less, further preferably 10 μmol / L or less, and particularly preferably 1 μmol / L or less.

[0100] (Analysis of compositions containing methyl methacrylate)

[0101] For example, GC-MS can be used to confirm that a composition containing methyl methacrylate contains components A, B, C, and water. In the GC-MS spectrum of the composition containing methyl methacrylate, if a peak appears at the same retention time as a standard for component A, and the m / z value of that peak, detected by mass spectrometry, matches the exact mass of component A, then the composition containing methyl methacrylate can be identified as containing component A. If a standard for component A is unavailable, and the mass spectrum of the peak appearing in the GC-MS spectrum of the composition containing methyl methacrylate matches the mass spectrum of component A recorded in a mass spectrometry database, then that peak can be identified as the peak of component A. That is, the composition containing methyl methacrylate can be identified as containing component A. Examples of mass spectrometry databases include NIST20, NIST17, NIST14, and NIST14s. Furthermore, if the volatility is too low to be detected by GC-MS, LC-MS can be used for detection. The presence of components B, C, and water can also be confirmed using the same method.

[0102] Furthermore, the concentration of methyl methacrylate can be quantified, for example, by performing a GC-FID determination of a composition containing methyl methacrylate and using the area percentage method, correcting for the moisture concentration quantified by a Karl Fischer moisture analyzer. The concentration of component A can be quantified, for example, by performing a GC determination of a composition containing methyl methacrylate and using the internal standard method. If a standard for component A is unavailable and quantification using the internal standard method is not possible, the concentration of any known organic compound can be determined by GC-FID under the same conditions as the composition containing methyl methacrylate, and the concentration of component A can be calculated using the following formula.

[0103]

[0104] Here, N is the number of carbon atoms in one molecule of an organic compound with a known concentration. A S represents the number of carbon atoms in one molecule of component A. A Let S be the peak area of ​​component A, S be the peak area of ​​the organic compound with known concentration, and M be the concentration (μmol / L) of the organic compound with known concentration.

[0105] In addition, when the volatility is low and quantification cannot be performed by GC, chromatographic methods such as LC can be used for quantification.

[0106] The concentrations of components B and C can also be calculated using the same method as for component A.

[0107] In addition, the presence and concentration of water in a composition containing methyl methacrylate can be confirmed using the Karl Fischer method.

[0108] [Method for manufacturing compositions containing methyl methacrylate]

[0109] As a method for manufacturing the composition containing methyl methacrylate of the present invention, a method of adding component A and component B to methyl methacrylate can be cited. Methyl methacrylate can be a commercially available product or methyl methacrylate manufactured by known methods such as the acetone cyanohydrin (ACH) method, the modified acetone cyanohydrin (new ACH) method, the C4 direct oxidation method, the direct methylation method, the ethylene method, or the modified ethylene method. Component A and component B can be commercially available products or self-made products synthesized using known methods. When using self-made products manufactured by known methods such as the acetone cyanohydrin (ACH) method, the modified acetone cyanohydrin (new ACH) method, the C4 direct oxidation method, the direct methylation method, the ethylene method, or the modified ethylene method, the composition containing methyl methacrylate can be manufactured by using component A or component B as a raw material or by adding them during the manufacturing process. Furthermore, if component A or component B is generated as a byproduct during the methyl methacrylate manufacturing process, the composition containing methyl methacrylate can be manufactured by retaining a portion of the generated component A or component B.

[0110] [Evaluation methods for storage stability and thermal stability]

[0111] The methyl methacrylate-containing compositions of the present invention exhibit high quality stability during storage. As a method for evaluating the quality stability of methyl methacrylate-containing compositions during storage, for example, a method can be cited to confirm the amount of methyl methacrylate dimer and methyl pyruvate formed by actually storing the methyl methacrylate-containing compositions for a long period. Alternatively, from the viewpoint of ease of operation, a method can be used to confirm the amount of methyl methacrylate dimer and methyl pyruvate formed by heating the methyl methacrylate-containing compositions for a short time. In the case of short-time heating, the heating temperature is preferably 50–100°C, and the heating time is preferably 1–24 hours. In the present invention, the quality stability of methyl methacrylate-containing compositions during storage is evaluated by measuring the amount of methyl methacrylate dimer and methyl pyruvate formed when the methyl methacrylate-containing compositions are stored at 25°C for 14 days.

[0112] [Manufacturing method of methyl methacrylate polymer]

[0113] The method for manufacturing the methyl methacrylate polymer of the present invention includes the following steps: polymerizing a polymerizable composition comprising the methyl methacrylate composition of the present invention.

[0114] <Polymerizable Compositions>

[0115] Polymerizable compositions may contain monomers and other additives that can be copolymerized with methyl methacrylate, as needed.

[0116] (Monomers that can be copolymerized with methyl methacrylate)

[0117] Examples of monomers that can copolymerize with methyl methacrylate include the following.

[0118] Ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, or benzyl methacrylate and other methacrylates;

[0119] Acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, or 2-ethylhexyl acrylate;

[0120] Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, or itaconic acid;

[0121] Maleic anhydride or itaconic anhydride and other unsaturated carboxylic anhydrides;

[0122] N-phenylmaleimide, or N-cyclohexylmaleimide, etc., maleimides;

[0123] Vinyl monomers containing hydroxyl groups, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or 2-hydroxypropyl methacrylate;

[0124] Vinyl acetate, or vinyl benzoate, and other vinyl esters;

[0125] Vinyl chloride, vinylidene chloride, and their derivatives;

[0126] Nitrogen-containing vinyl monomers such as methacrylamide or acrylonitrile;

[0127] Monomers containing epoxy groups, such as glycidyl acrylate or glycidyl methacrylate;

[0128] Styrene, or aromatic vinyl monomers such as α-methylstyrene;

[0129] Ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate and other alkyl diol di(meth)acrylates;

[0130] 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 and other polyoxyalkylene glycol di(meth)acrylates;

[0131] Vinyl monomers such as divinylbenzene that have more than two olefinic unsaturated bonds in their molecules;

[0132] An unsaturated polyester prepolymer obtained from at least one polycarboxylic acid containing an olefinic unsaturated polycarboxylic acid and at least one diol;

[0133] Vinyl ester prepolymer obtained by modifying the epoxy group ends with acrylic acid;

[0134] Of the above, the monomers that can copolymerize with methyl methacrylate are preferably selected from at least one of methyl methacrylate and acrylate. Thus, a methyl methacrylate polymer with an excellent balance of transparency, heat resistance, and moldability can be obtained by polymerizing the polymerizable composition. The monomers that can copolymerize with methyl methacrylate are more preferably acrylates, and particularly preferably at least one selected from methyl acrylate, ethyl acrylate, and n-butyl acrylate.

[0135] It should be noted that the monomers that can be copolymerized with methyl methacrylate can be one or more. Furthermore, if component A is a monomer that can be copolymerized with methyl methacrylate, component A can be used as the monomer that can be copolymerized with methyl methacrylate, or a different monomer that can be copolymerized with methyl methacrylate can be used.

[0136] In the polymerizable composition, the content of monomers that can copolymerize with methyl methacrylate is preferably 0 to 50 parts by weight relative to 100 parts by weight of methyl methacrylate. This results in a methyl methacrylate polymer with high transparency. The upper limit of the content of monomers that can copolymerize with methyl methacrylate is more preferably 40 parts by weight or less, and even more preferably 30 parts by weight or less, relative to 100 parts by weight of methyl methacrylate. The lower limit of the content of monomers that can copolymerize with methyl methacrylate is more preferably 0.01 parts by weight or more, even more preferably 0.1 parts by weight or more, and particularly preferably 1 part by weight or more, relative to 100 parts by weight of methyl methacrylate.

[0137] (Other additives)

[0138] As other additives, polymerization initiators are preferred. Additionally, chain transfer agents, release agents, lubricants, plasticizers, antioxidants, antistatic agents, light stabilizers, UV absorbers, flame retardants, flame retardant accelerants, polymerization inhibitors, fillers, pigments, dyes, silane coupling agents, leveling agents, defoamers, fluorescent agents, etc., may be included as needed. It should be noted that there may be one or more of these other additives.

[0139] Examples of polymerization initiators include the following compounds.

[0140] Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis(2,4,4-trimethylpentane), 2-2'-azobis(2-methylpropane), 1,1'-azobis(cyclohexanecarboxynitrile), and dimethyl 2,2'-azobisisobutyrate;

[0141] Benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane, 1,1-bis(tert-butylperoxide)cyclohexane, 1,1-bis(tert-butylperoxide)-3,5,5-trimethylcyclohexane, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide isobutyrate, tert-butyl peroxide benzoate, tert-hexyl peroxide benzoate, tert-butyl peroxide isopropyl monocarbonate, tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxide silicate, tert-butyl peroxide acetate, tert-hexyl peroxide isopropyl monocarbonate, 2-ethyl peroxide Organic peroxides include tert-hexyl hexanoate, tert-amyl peroxide-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, and dilauryl peroxide.

[0142] Potassium persulfate and other persulfate compounds;

[0143] Redox polymerization initiators;

[0144] Of the above, from the viewpoint of preserving stability and reactivity with methyl methacrylate, the polymerization initiator is preferably selected from at least one of azo compounds and organic peroxides.

[0145] The amount of polymerization initiator used is preferably 0.0001 to 1 part by mass relative to 100 parts by mass of methyl methacrylate and monomers that can copolymerize with methyl methacrylate.

[0146] <Polymerization Methods for Polymerizable Compositions>

[0147] Examples of polymerization methods include bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. From the viewpoint of environmental impact caused by the use of solvents and the transparency of the resulting methyl methacrylate polymer, bulk polymerization is preferred.

[0148] There are no particular limitations on the specific method of bulk polymerization. Well-known injection molding polymerization methods such as unit casting or continuous casting can be used to manufacture it.

[0149] Injection molding polymerization is a method of injecting a polymeric composition into a mold consisting of two inorganic glass or metal plates (e.g., SUS plates) that are sealed around their perimeter with gaskets such as soft resin tubes and arranged opposite each other at a specified interval, and allowing them to polymerize to obtain methyl methacrylate polymers.

[0150] There are no particular limitations on the mold used for injection molding; any known mold can be used. For example, a mold for unit pouring can be made by arranging two plate-like bodies, such as inorganic glass, chrome-plated metal, or stainless steel, at a predetermined interval and placing washers at their edges, thus forming a sealed space between the plate-like bodies and the washers. For continuous pouring, a mold can be made by forming a sealed space between the opposing faces of a pair of annular belts traveling in the same direction at the same speed and washers traveling at the same speed as the annular belts on both sides of the annular belts.

[0151] The gaps in the mold are appropriately adjusted to obtain a resin plate of the desired thickness, typically 1–30 mm.

[0152] The polymerization temperature is preferably 125–210°C. This allows for a suitable polymerization rate. The lower limit of the polymerization temperature is more preferably 130°C or higher, and the upper limit is more preferably 180°C or lower. The polymerization time is not particularly limited, and can be, for example, 0.5–24 hours.

[0153] Example

[0154] The present invention will now be described in detail with reference to embodiments and comparative examples, but the present invention is not limited to these embodiments. Unless otherwise specified, “%” and “ppm” in the embodiments and comparative examples refer to “weight %” and “weight ppm”.

[0155] The water concentration in the methyl methacrylate reagent was calculated using the Karl Fischer method. The composition of the methyl methacrylate-containing composition before storage was calculated based on the amount of each raw material added. After storage, the methyl methacrylate dimer and methyl pyruvate in the methyl methacrylate-containing composition were quantified using GC-MS via an absolute standard curve method. The GC-MS determination conditions are shown below.

[0156] Apparatus: GC-MS measuring apparatus (product name: QP-2010SE, manufactured by Shimadzu Corporation)

[0157] [GC Conditions]

[0158] Pillar (Product name: DB-WAX, manufactured by Agilent Technologies)

[0159] Length: 60m, Inner diameter: 0.32mm, Film thickness: 1.00μm

[0160] Injection volume: 1.0 μL

[0161] Vaporization chamber temperature: 210℃

[0162] Column oven temperature: Hold at 35℃ for 10 minutes, increase from 35℃ to 150℃ at 5℃ / min, hold at 150℃ for 17 minutes, increase from 150℃ to 220℃ at 5℃ / min, and hold at 220℃ for 6 minutes.

[0163] Carrier gas: Helium

[0164] Injection mode: Split (split ratio 50)

[0165] Control mode: Constant linear velocity (25.0 cm / s)

[0166] Pressure: 26.1 kPa

[0167] Total flow rate: 52.5 mL / min

[0168] Purge flow rate: 3.0 mL / min

[0169] Column flow rate: 0.97 mL / min

[0170] [MS conditions]

[0171] Ionization method: EI (Electron Ionization)

[0172] Ion source temperature: 250℃

[0173] Interface temperature: 250℃

[0174] m / z detection range: 10~300

[0175] Testing time: 70 minutes

[0176] The quantitative determination of moisture concentration based on the Karl Fischer method is performed using an automatic moisture measuring device (product name: AQV-2200, manufactured by Hiranuma Kogyo Co., Ltd.).

[0177] (Example 1)

[0178] Using methacrylonitrile as component A, 0.0229 g of component A was added to 10.0275 g of reagent methyl methacrylate (water concentration 240 ppm) to prepare a methyl methacrylate solution (solution A-1). The concentration of component A in this solution A-1 is shown in Table 1.

[0179] Using 2,4-dimethyl-6-tert-butylphenol as component B, 0.0228 g of component B was added to 10.0026 g of methyl methacrylate (water concentration 240 ppm) to prepare a methyl methacrylate solution (solution B-1). The concentration of component B in this solution B-1 is shown in Table 1.

[0180] Next, 0.10016 g of solution A-1 and 0.1027 g of solution B-1 were added to 20.0053 g of methyl methacrylate (moisture concentration 240 ppm) to prepare a composition containing methyl methacrylate. The concentrations of each component in this composition containing methyl methacrylate are shown in Table 2.

[0181] The resulting composition containing methyl methacrylate was stored at 25°C for 14 days. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition are shown in Table 2.

[0182] (Examples 2-5)

[0183] Using the compounds shown in Table 1 as component A, and varying the amounts of reagent methyl methacrylate and component A as shown in Table 1, solution A-1 was prepared in the same manner as in Example 1.

[0184] B-1 solution was prepared using the same method as in Example 1.

[0185] Next, the amounts of methyl methacrylate, solution A-1, and solution B-1 were varied as shown in Table 2, and the composition containing methyl methacrylate was prepared in the same manner as in Example 1. The concentrations of each component in the composition containing methyl methacrylate are shown in Table 2.

[0186] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0187] (Examples 6-10)

[0188] Using the compounds shown in Table 1 as component A, and varying the amounts of reagent methyl methacrylate and component A as shown in Table 1, solution A-1 was prepared in the same manner as in Example 1.

[0189] As shown in Table 1, the amounts of reagent methyl methacrylate and component B were changed, and solution B-1 was prepared in the same manner as in Example 1.

[0190] Next, the amounts of methyl methacrylate, solution A-1, and solution B-1 were varied as shown in Table 2, and the composition containing methyl methacrylate was prepared in the same manner as in Example 1. The concentrations of each component in the composition containing methyl methacrylate are shown in Table 2.

[0191] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0192] (Examples 11-17)

[0193] Liquid A-1 was prepared using the same method as in Example 1.

[0194] Using the compounds shown in Table 1 as component B, and varying the amounts of reagent methyl methacrylate and component B as shown in Table 1, solution B-1 was prepared in the same manner as in Example 1.

[0195] Next, the amounts of methyl methacrylate, solution A-1, and solution B-1 were varied as shown in Table 2, and the composition containing methyl methacrylate was prepared in the same manner as in Example 1. The concentrations of each component in the composition containing methyl methacrylate are shown in Table 2.

[0196] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0197] (Example 18)

[0198] Liquid A-1 and liquid B-1 were prepared using the same method as in Example 1.

[0199] Next, the amounts of methyl methacrylate, solution A-1, and solution B-1 were varied as shown in Table 2, and the composition containing methyl methacrylate was prepared in the same manner as in Example 1. The concentrations of each component in the composition containing methyl methacrylate are shown in Table 2.

[0200] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0201] (Example 19)

[0202] Liquid A-1 was prepared using the same method as in Example 1.

[0203] As shown in Table 1, the amounts of reagent methyl methacrylate and component B were changed, and solution B-1 was prepared in the same manner as in Example 1.

[0204] Next, the amounts of methyl methacrylate, solution A-1, and solution B-1 were varied as shown in Table 2, and the composition containing methyl methacrylate was prepared in the same manner as in Example 1. The concentrations of each component in the composition containing methyl methacrylate are shown in Table 2.

[0205] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0206] (Example 20)

[0207] B-1 solution was prepared using the same method as in Example 1.

[0208] Next, using methacrylonitrile as component A, 0.0229 g of component A and 0.1090 g of solution B-1 were added to 20.0100 g of reagent methyl methacrylate (moisture concentration 240 ppm) to prepare a composition containing methyl methacrylate. The concentrations of each component in this composition containing methyl methacrylate are shown in Table 2.

[0209] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0210] (Examples 21-22)

[0211] Liquid A-1 was prepared using the same method as in Example 1.

[0212] As shown in Table 1, the amounts of reagent methyl methacrylate and component B were changed, and solution B-1 was prepared in the same manner as in Example 1.

[0213] Next, the amounts of methyl methacrylate, solution A-1, and solution B-1 were varied as shown in Table 2, and the composition containing methyl methacrylate was prepared in the same manner as in Example 1. The concentrations of each component in the composition containing methyl methacrylate are shown in Table 2.

[0214] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0215] (Comparative Example 1)

[0216] B-1 solution was prepared using the same method as in Example 1.

[0217] Next, 0.2213 g of solution B-1 was added to 40.0273 g of methyl methacrylate (water concentration 240 ppm) to prepare a composition containing methyl methacrylate. The concentrations of each component in this composition containing methyl methacrylate are shown in Table 2.

[0218] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0219] (Comparative Example 2)

[0220] 40.0000 g of methyl methacrylate (moisture concentration 240 ppm) was used as the composition containing methyl methacrylate and stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0221] (Comparative Example 3)

[0222] B-1 solution was prepared using the same method as in Example 1.

[0223] Using diacetyl as component C, 0.0205 g of component C was added to 9.9913 g of reagent methyl methacrylate (water concentration 240 ppm) to prepare a methyl methacrylate solution (C-1 solution). The concentration of component C in this C-1 solution is shown in Table 1.

[0224] Next, 0.2151 g of solution B-1 and 0.2069 g of solution C-1 were added to 40.0218 g of methyl methacrylate (moisture concentration 240 ppm) to prepare a composition containing methyl methacrylate. The concentrations of each component in this composition containing methyl methacrylate are shown in Table 2.

[0225] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0226] (Comparative Example 4)

[0227] Liquid A-1 was prepared using the same method as in Example 1.

[0228] Next, 0.2054 g of solution A-1 was added to 40.0249 g of methyl methacrylate (water concentration 240 ppm) to prepare a composition containing methyl methacrylate. The concentrations of each component in this composition containing methyl methacrylate are shown in Table 2.

[0229] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0230] (Comparative Example 5)

[0231] Liquid A-1 was prepared using the same method as in Example 1.

[0232] As shown in Table 1, the amounts of reagent methyl methacrylate and component B were changed, and solution B-1 was prepared in the same manner as in Example 1.

[0233] Next, 0.1010 g of solution A-1, 0.1051 g of solution B-1, and 0.3003 g of pure water were added to 20.0192 g of methyl methacrylate (water concentration 240 ppm) to prepare a composition containing methyl methacrylate. The concentrations of each component in this composition containing methyl methacrylate are shown in Table 2.

[0234] The resulting composition containing methyl methacrylate was stored in the same manner as in Example 1. The amounts of methyl methacrylate dimer and methyl pyruvate formed in the stored composition containing methyl methacrylate are shown in Table 2.

[0235] Table 1

[0236]

[0237] Table 2

[0238]

[0239] Industrial availability

[0240] According to the present invention, compositions containing methyl methacrylate that can be used in raw materials such as acrylic resins can be stably preserved for a long period of time, which is useful in industry.

Claims

1. A composition containing methyl methacrylate, comprising methyl methacrylate, a nitrile compound (component A), and a polymerization inhibitor (component B), The concentration of methyl methacrylate is 99–99.99% by mass. The nitrile compound is selected from one or more of acetonitrile, propionitrile, acrylonitrile, benzonitrile, cyclohexaneformitrile, 3-hydroxypropionitrile, 3-methoxypropionitrile, 2-hydroxypropionitrile, 2-aminopropionitrile, 4-cyanophenol, 4-aminobenzonitrile, 4'-cyanoacetophenone, and 4-(methylthio)benzonitrile.

2. The composition containing methyl methacrylate according to claim 1, wherein, When the concentration of component A is set as MA in μmol / L and the concentration of component B is set as MB in μmol / L, the MB / MA ratio is greater than 0.

003.

3. The composition containing methyl methacrylate according to claim 1, wherein, When the concentration of component A is set as MA and the unit is μmol / L, MA is 1 to 20000 μmol / L.

4. The composition containing methyl methacrylate according to claim 3, wherein, The MA is 10–15000 μmol / L.

5. The composition containing methyl methacrylate according to claim 1, wherein, When the concentration of component B is set as MB and the unit is μmol / L, MB is 1 to 5000 μmol / L.

6. The composition containing methyl methacrylate according to claim 5, wherein, The MB concentration is 10–2500 μmol / L.

7. The composition containing methyl methacrylate according to claim 1, wherein, The molecular weight of component A is below 1000.

8. The composition containing methyl methacrylate according to claim 1, wherein, Component B is a polymerization inhibitor selected from at least one of phenolic compounds, quinone compounds, nitrobenzene compounds, nitroso radical compounds, amine compounds, phosphorus-containing compounds, sulfur-containing compounds, iron-containing compounds, copper-containing compounds, and manganese-containing compounds.

9. The composition containing methyl methacrylate according to claim 1, wherein, Component B is a polymerization inhibitor selected from phenolic compounds, nitrile radical compounds, amine compounds, phosphorus-containing compounds, and sulfur-containing compounds.

10. The composition containing methyl methacrylate according to claim 1, wherein, Component B is a polymerization inhibitor selected from hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, N,N-diphenylamine, N-nitrosodiphenylamine, triphenyl phosphite, and phenothiazine.

11. The composition containing methyl methacrylate according to claim 1, wherein, The concentration of methyl methacrylate is 99.8%–99.99% by mass.

12. The composition containing methyl methacrylate according to claim 1, wherein, It does not contain diacetyl, or the concentration of diacetyl it contains is less than 55 μmol / L.

13. A method for manufacturing a methyl methacrylate polymer, comprising the following steps: polymerizing a polymerizable composition comprising the composition containing methyl methacrylate as described in any one of claims 1 to 12.

14. The method for manufacturing the methyl methacrylate polymer according to claim 13, wherein, The polymerizable composition contains monomers that can be copolymerized with methyl methacrylate.

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