JP2015000849A - Amine adduct of 1,4-naphthohydroquinone-2-sulfonamide and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an amine adduct that has a low sublimability, and is useful as a polymerization inhibitor for a vinyl monomer.SOLUTION: This invention provides an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide represented by general formula (1) and a polymerization inhibitor comprising the adduct. (In the general formula (1), an amine represents a primary amine compound, a secondary amine compound, a tertiary amine compound, an amidine compound or a guanidine compound, and n represents 1 or 2).

Description

The present invention relates to an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide useful as a polymerization inhibitor for vinyl monomers.

Conventional polymerization inhibitors for vinyl monomers include hydroquinone, p-methoxyphenol, phenols such as 2,6-di-t-butylphenol, amines such as phenothiazine and methylene blue, copper salts such as copper dibutyldithiocarbamate, etc. Various compounds such as nitro compounds, nitroso compounds, and N-oxyl compounds are known. In particular, methoquinone and hydroquinone are often used (for example, Patent Documents 1 to 4).

Various naphthoquinone compounds are also known to be effective as polymerization inhibitors. For example, alkylated naphthoquinone compounds (for example, Patent Document 5) and 2-hydroxy-1,4-naphthoquinone (for example, Patent Document 6) are known as polymerization inhibitors for aromatic vinyl compounds, and the former. In this case, the orthoquinone compound is considered to be superior to the paraquinone compound. Further, 1,4-naphthoquinone and the like are known as polymerization inhibitors for vinyl acetate (for example, Patent Document 7), and 1,2-naphthoquinone is known as a polymerization inhibitor for (meth) acrylic acid and esters. (For example, Patent Document 8).

JP 09-255642 A JP 07-316164 A Japanese Patent Publication No. 2006-503159 Japanese Patent Laid-Open No. 08-109155 JP-A 63-235390 JP-A-56-86123 JP 2003-89706 A JP 09-316022 A

However, hydroquinone and methoquinone have high sublimation properties due to their low molecular weight, and there is a risk of mixing into the monomer during distillation of the monomer. In addition, considering that hydroquinone and methoquinone are benzene monocyclic causes high sublimation, 1,4-naphthohydroquinone and 4-alkoxy having a bicyclic naphthalene skeleton as in the above example Naphthol is also being studied. However, none of them has completely suppressed sublimation property, and further, a polymerization inhibitor having sublimation resistance has been demanded. Moreover, although the compound which substituted the sulfonamide group to 1, 4- naphthohydroquinone showed high sublimation resistance, the performance as a polymerization inhibitor was scarce.

Therefore, as a result of intensive studies on the structure and reactivity of 1,4-naphthohydroquinone-2-sulfonamide compound, the present inventors have found that an adduct of 1,4-naphthohydroquinone-2-sulfonamide compound and an amine compound is a vinyl monomer. The present invention was completed by finding out that it is effective as a polymerization inhibitor.

The first invention resides in an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide represented by the following general formula (1).

(In general formula (1), amine represents a primary amine compound, a secondary amine compound, a tertiary amine compound, an amidine compound or a guanidine compound, and n represents 1 or 2.)

The second invention resides in the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide according to the first invention, wherein the amine in the general formula (1) is a tertiary amine compound or an amidine compound.

The third invention is a 1,4-naphthohydroquinone-2-sulfonamide represented by the following structural formula (2) and an amine, and 1,4-naphthohydroquinone-2- represented by the general formula (1). A method for producing an amine adduct of sulfonamide exists.

A fourth invention resides in a polymerization inhibitor containing an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide described in the first or second invention.

A fifth invention resides in a vinyl monomer composition comprising a polymerization inhibitor containing a vinyl monomer and an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide described in the fourth invention. .

According to a sixth invention, the vinyl monomer is an α, β-unsaturated carboxylic acid compound, an α, β-unsaturated carboxylic acid ester compound or an aromatic vinyl compound. It resides in a vinyl monomer composition.

A seventh invention resides in a method for inhibiting the polymerization of a vinyl monomer, which comprises using a polymerization inhibitor containing the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide described in the fourth invention.

The eighth invention is the vinyl monomer according to the seventh invention, wherein the amount of the polymerization inhibitor containing an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide is 1 ppm or more and 1000 ppm or less with respect to the vinyl monomer. In the method of prohibiting polymerization.

The amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention has a high effect as a polymerization inhibitor for vinyl monomers, and has lower sublimation properties than conventional polymerization inhibitors for vinyl monomers. It is an industrially useful compound.

3 is an IR spectrum chart of 1,4-naphthohydroquinone-2-sulfonamide obtained in Synthesis Example 1. FIG. 2 is a ¹ H-NMR spectrum chart of 1,4-naphthohydroquinone-2-sulfonamide obtained in Synthesis Example 1. FIG. 2 is a mass spectrum chart of 1,4-naphthohydroquinone-2-sulfonamide obtained in Synthesis Example 1. FIG.

<Compound>
The amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention is a compound having a structure represented by the following general formula (1).

In general formula (1), amine represents a primary amine compound, a secondary amine compound, a tertiary amine compound, an amidine compound or a guanidine compound, and n represents 1 or 2.

Examples of the primary amine compound include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, benzylamine, phenethylamine and the like.

Examples of the secondary amine compound include aliphatic amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, piperidine, dibenzylamine, and diphenethylamine. In addition, alicyclic amines such as pyrrolidine, piperidine, hexamethyleneimine, and morpholine can also be used. Is mentioned.

The tertiary amine compounds include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tribenzylamine, Aliphatic amines such as triphenethylamine are listed. Further, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, N-methylmorpholine, N-butylmorpholine, N, N ′ -Cycloaliphatic amines such as dimethylpiperazine and N, N'-diethylpiperazine can also be used.

In addition, amidine compounds such as 1,5-diazabicyclo (4,3,0) -5-nonene and 1,8-diazabicyclo [5,4,0] -7-undecene, methyltriazabicyclodecene, triazabicyclo Guanidine compounds such as decene and tetramethylguanidine are also preferably used.

The following compounds are mentioned as a typical compound represented by General formula (1). That is, when the amine is a primary amine compound, methylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, ethylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, 1,4-naphtho Hydroquinone-2-sulfonamide propylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide butylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide pentylamine adduct, 1,4-naphtho Hexylamine adduct of hydroquinone-2-sulfonamide, heptylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, octylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, 1,4- Decylamine addition of naphthohydroquinone-2-sulfonamide 1,4-naphthohydroquinone-2-sulfonamide dodecylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide benzylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide phenethylamine adduct Etc.

When the amine is a secondary amine compound, 1,4-naphthohydroquinone-2-sulfonamide dimethylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide diethylamine adduct, 1,4-naphthohydroquinone- 2-sulfonamide dipropylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide dibutylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide dipentylamine adduct, 1,4-naphtho Hexylamine adduct of hydroquinone-2-sulfonamide, diheptylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, dioctylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, 1,4 -Naphthohydroquinone-2-sulfonamide with didecylamine , 1,4-naphthohydroquinone-2-sulfonamide didodecylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide dibenzylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide Examples include diphenethylamine adducts, piperidine adducts of 1,4-naphthohydroquinone-2-sulfonamide, and morpholine adducts of 1,4-naphthohydroquinone-2-sulfonamide.

When the amine is a tertiary amine compound, trimethylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, triethylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, 1,4-naphthohydroquinone-2 -Tripropylamine adduct of sulfonamide, tributylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, tripentylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, 1,4-naphtho Trihexylamine adduct of hydroquinone-2-sulfonamide, triheptylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, trioctylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide, 1 , 4-Naphthohydroquinone-2-sulfonamide Tridecylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide tridodecylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide tribenzylamine adduct, 1,4-naphthohydroquinone-2 -Sulphonamide triphenethylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide N-methylpiperidine adduct, and the like.

When the amine is an amidine compound, 1,8-diazabicyclo [5,4,0] -7-undecene adduct of 1,4-naphthohydroquinone-2-sulfonamide, 1,4-naphthohydroquinone-2-sulfonamide 1,5-diazabicyclo (4,3,0) -5-nonene adduct, etc., and when the amine is a guanidine compound, methyltriazabicyclodecene addition of 1,4-naphthohydroquinone-2-sulfonamide Products, 1,4-naphthohydroquinone-2-sulfonamide triazabicyclodecene adduct, 1,4-naphthohydroquinone-2-sulfonamide tetramethylguanidine adduct, and the like.

Among these exemplified compounds, 1,4-naphthohydroquinone-2-sulfonamide tributylamine adduct, 1,4-naphthohydroquinone, whose amine is a tertiary amine, in that it is highly effective as a polymerization inhibitor. 2-sulfonamide trihexylamine adduct, 1,4-naphthohydroquinone-2-sulfonamide trioctylamine adduct, and 1,4-naphthohydroquinone-2-sulfonamide in which the amine is an amidine compound 1,8-diazabicyclo [5,4,0] -7-undecene adduct is preferred.

The amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention is different from 1,4-naphthohydroquinone and 4-alkoxynaphthol, which are known naphthalene polymerization inhibitors, It has a sulfonamide group in the skeleton and has a low sublimation property.

<Production method>
Next, the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention is obtained by reacting 1,4-naphthohydroquinone-2-sulfonamide with an amine as shown in the following reaction formula. Can be obtained.

(In the above reaction formula and general formula (1), amine represents a primary amine compound, secondary amine compound, tertiary amine compound, amidine compound or guanidine compound, and n represents 1 or 2.)

The 1,4-naphthohydroquinone-2-sulfonamide represented by the structural formula (2) can be obtained by reacting 1,4-naphthohydroquinone-2-sulfonate with ammonium bisulfite.

1,4-Naphthohydroquinone-2-sulfonate is an addition reaction between a naphthoquinone compound and bisulfite, for example, naphthoquinone in an aqueous solution containing bisulfite as described in JP-A-60-146865. It can be obtained by adding the compound with stirring at room temperature.

1,4-naphthohydroquinone-2-sulfonic acid salt is obtained in the form of a salt that varies depending on the type of the bisulfite salt used in the addition reaction. For example, sodium 1,4-naphthohydroquinone-2-sulfonate can be obtained by using sodium hydrogen sulfite, and potassium 1,4-naphthohydroquinone-2-sulfonate can be obtained by using potassium hydrogen sulfite. By using ammonium, 1,4-naphthohydroquinone-2-sulfonic acid ammonium is obtained. In any salt, 1,4-naphthohydroquinone-2-sulfonamide can be obtained by an amidation reaction described below.

Next, 1,4-naphthohydroquinone-2-sulfonamide represented by the general formula (2) can be obtained by reacting the 1,4-naphthohydroquinone-2-sulfonate with ammonium bisulfite. .

The reaction between 1,4-naphthohydroquinone-2-sulfonate and ammonium bisulfite is carried out in an aqueous solution.

Crystals of 1,4-naphthohydroquinone-2-sulfonamide are obtained by dissolving 1,4-naphthohydroquinone-2-sulfonate in water, adding an aqueous solution of ammonium bisulfite to the aqueous solution, and heating the mixed solution. Can be obtained.

The temperature of the amidation reaction is preferably 40 ° C. or more and less than 90 ° C. When the temperature is less than 40 ° C., the reaction hardly proceeds, whereas when it is 90 ° C. or more, the produced 1,4-naphthohydroquinone-2-sulfonamide is Since it decomposes and a by-product increases, it is not preferable.

Further, since ammonium bisulfite has a structure in which ammonium bisulfite is dehydrated and dimerized, the higher the concentration of the aqueous ammonium bisulfite solution added, the more advantageous is the production of 1,4-naphthohydroquinone-2-sulfonamide. Specifically, the concentration of the ammonium bisulfite aqueous solution is preferably 20% by weight or more, particularly preferably 60% by weight or more.

In addition, the higher the concentration of the 1,4-naphthohydroquinone-2-sulfonate aqueous solution, the more easily the 1,4-naphthohydroquinone-2-sulfonamide produced is crystallized in the reaction solution, and the isolation Since it becomes easy, it is preferable. Specifically, the concentration of the aqueous solution of 1,4-naphthohydroquinone-2-sulfonate is preferably in the range of 20 to 60% by weight.

The amidation reaction can be performed in an inert gas atmosphere or in the presence of air, but 1,4-naphthohydroquinone-2-sulfonate as a raw material and / or 1,4-naphtho as a product. Since hydroquinone-2-sulfonamide may be oxidized to produce impurities, it is preferably carried out in an inert gas atmosphere.

The 1,4-naphthohydroquinone-2-sulfonamide thus obtained can be obtained as a white solid having high crystallinity and high purity.

Next, an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide can be obtained by adding an amine to the obtained 1,4-naphthohydroquinone-2-sulfonamide and reacting it.

The addition molar ratio of amine to 1,4-naphthohydroquinone-2-sulfonamide is preferably 1 or more and 2 or less. If the addition ratio is less than 1, the isolation yield of the adduct is low, and if the addition ratio exceeds 2, the product has increased solubility due to a large amount of base remaining in the reaction solution. The rate decreases, which is not preferable.

In the reaction with amine, a solvent is usually used. The solvent is not particularly limited, but aromatic solvents such as toluene, xylene, chlorobenzene, and methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ether solvents such as tetrahydrofuran, diethyl ether, and dibutyl ether Alkane solvents such as n-hexane and n-heptane are preferably used.

The reaction temperature is usually room temperature. Specifically, it is preferably 10 ° C. or higher and 50 ° C. or lower. If it is less than 10 ° C., the formation of an addition product is slow, whereas if it exceeds 50 ° C., amine may be eliminated, which is not preferable.

When using an aromatic solvent such as toluene or an alkane solvent such as n-hexane as the amidation reaction solvent, 1,4-naphthohydroquinone-2-sulfonamide used as a raw material was also obtained by the reaction. Both amine adducts of 4-naphthohydroquinone-2-sulfonamide are insoluble in the solvent and the reaction is in the form of a slurry throughout, but the reaction slurry is subjected to suction filtration and drying to obtain 1,4-naphthohydroquinone. Crystals of amine adducts of 2-sulfonamide can be obtained.

Although depending on the reaction conditions, the addition ratio of amine in the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide is mainly 1 amine per molecule of 1,4-naphthohydroquinone-2-sulfonamide. Although it is a molecule, it may be a mixture of a single molecule adduct and a two molecule adduct depending on the type of amine used. In that case, it is possible to purify and isolate only the one-molecule adduct and use it for the application of the present invention. However, even a mixture of the one-molecule adduct and the two-molecule adduct is used for the application of the present invention. And exhibits an effect as a polymerization inhibitor.

<Polymerization inhibitor>
The amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention effectively acts as a polymerization inhibitor for vinyl monomers. By adding the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention to a vinyl monomer, unintended polymerization is prevented at the time of monomer production, purification, modification, storage, transportation, etc. Can be handled stably.

Usable vinyl monomers include α, β-unsaturated carboxylic acid compounds such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acid ester compounds such as acrylic acid ester and methacrylic acid ester, acrylonitrile, vinyl acetate, Aromatic vinyl compounds such as styrene can be mentioned. Acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, ditrimethylolpropane tetra Examples thereof include acrylate and 2-hydroxy-3-phenoxypropyl acrylate. Examples of the methacrylic acid ester include methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and the like.

<Composition>
The vinyl monomer composition of the present invention contains at least the vinyl monomer and an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention which is a polymerization inhibitor. The form and content of the vinyl monomer are not particularly limited. For example, a vinyl monomer itself or a monomer solution can be used.

Moreover, the polymerization inhibitor containing the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention is a 1,4-naphthohydroquinone-2-sulfone of the present invention as long as the effects of the present invention are not impaired. Other components such as polymerization inhibitors other than the amine adduct of amide may be contained. Such other components are not particularly limited, and examples thereof include known compounds as polymerization inhibitors.

For example, at least one compound selected from a phenol polymerization inhibitor, a thioether polymerization inhibitor, an amine polymerization inhibitor, a nitroso polymerization inhibitor, an N-oxyl compound, and molecular oxygen may be contained.

Examples of the phenol polymerization inhibitor include hydroquinone, 4-methoxyphenol, cresol, tert-butylcatechol, 3,5-di-tert-butyl-4-hydroxytoluene, 2,2′-methylenebis (4-methyl-6). -Tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 1-methoxy-4-naphthol and the like. It is done.

Examples of the thioether polymerization inhibitor include phenothiazine, distearyl thiodipropionate, and the like.

Examples of amine polymerization inhibitors include p-phenylenediamine, 4-aminodiphenylamine, N, N′-diphenyl-p-phenylenediamine, Ni-propyl-N′-phenyl-p-phenylenediamine, and N- ( 1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N, N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4,4′-dic Mildiphenylamine, 4,4′-dioctyldiphenylamine and the like can be mentioned.

Examples of the nitroso polymerization inhibitor include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol and the like. .

Examples of N-oxyl compounds include piperidine-1-oxyl, pyrrolidine-1-oxyl, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, 2,2,6,6-tetra And nitroxides such as methylpiperidine-1-oxyl.

Moreover, the composition of the polymerization inhibitor may further contain a copper salt compound and / or a manganese salt compound. Examples of such compounds include copper salts such as copper dialkyldithiocarbamate, copper acetate, copper salicylate, copper thiocyanate, copper nitrate, copper chloride, copper carbonate, copper hydroxide, and copper acrylate; manganese dialkyldithiocarbamate, diphenyl Examples include manganese dithiocarbamate, manganese formate, manganese acetate, manganese octoate, manganese naphthenate, manganese permanganate, and a manganese salt of ethylenediaminetetraacetic acid.

These other components can be used alone or in combination of two or more with respect to the polymerization inhibitor of the present invention. These other components can be appropriately selected according to the type and application of the monomer to be applied.

<Polymerization prohibition method>
When the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide of the present invention is used as a polymerization inhibitor for vinyl monomers, the polymerization method may be either thermal polymerization or photopolymerization, and a polymerization initiator is used. Polymerization can be efficiently inhibited whether or not it is used.

The addition amount of the polymerization inhibitor of the present invention with respect to the vinyl monomer is 1 ppm or more and 1000 ppm or less, preferably 30 ppm or more and 200 ppm or less. As an addition method, the powder may be added to the vinyl monomer as it is, or may be added after being dissolved in a solvent.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

The product was confirmed by measurement with the following equipment.
(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Infrared (IR) spectrophotometer: Model IR-810 manufactured by JASCO Corporation
(3) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model JNM ECS 400 type FT NMR Spectrometer
(4) Mass spectrum: manufactured by Shimadzu Corporation, mass spectrometer, model GCMS-QP5000

(Synthesis Example 1) 37 g of 1,4-naphthohydroquinone-2-sulfonic acid ammonium salt solution having a concentration of 45% by weight was charged into a thick sample tube having a synthesis capacity of 1,4-naphthohydroquinone-2-sulfonamide of 200 ml. . The sample tube was equipped with a silicon rubber stopper set with an air cooling tube for cooling evaporating water, a temperature sensor and a glass tube for blowing nitrogen gas, and heated to 55 ° C. while aeration of nitrogen gas at a flow rate of 0.2 ml / min. Thereafter, 41 g of a 60 wt% ammonium bisulfite stock solution (68 wt% as ammonium hydrogen sulfite) was added into the sample tube, and the mixture was heated and stirred for 4 hours. The crystal slurry of the reaction product was stored overnight at room temperature, and the next day, Suction filtration was performed using 5C filter paper to obtain about 4 g of crude 1,4-naphthohydroquinone-2-sulfonamide crystals. Since the crystals contained ammonium 1,4-naphthohydroquinone-2-sulfonate as a raw material, the crystals were purified by reslurry with 100 ml of ion-exchanged water and then filtered. This operation was repeated twice. The washed crystal was washed with 100 ml of acetone and then dried at 60 ° C. under reduced pressure for 2 hours. The dried white crystals were pulverized in a glass mortar to obtain 2.5 g of a purified product 1,4-naphthohydroquinone-2-sulfonamide. The purity of the purified product was 99.2% as a result of evaluation as a percentage of peak area by HPLC.

(1) Melting point: 260 ° C. or higher (2) IR spectrum (KBr tablet method): see FIG. 1 (3) ¹ H-NMR (400 MHz, solvent DMSO-d ₆ ): see FIG. 2 (4) mass spectrum (LC / MS): See FIG.

(Synthesis Example 1) 1,4-Naphthohydroquinone-2-sulfonamide butylamine adduct synthesis 1,4 Obtained in a 100 ml three-necked flask equipped with a stirrer and thermometer in the same manner as in Synthesis Example 1 under a nitrogen atmosphere -2.39 g (10 mmol) of naphthohydroquinone-2-sulfonamide was slurried in 15 g of degassed toluene and then 0.87 g (12 mmol) of n-butylamine was added. After stirring for 30 minutes, 10 g of n-hexane was added, and the resulting white slurry was suction filtered and dried to obtain 2.30 g of a butylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide as a white powder. The isolation yield based on the raw material 1,4-naphthohydroquinone-2-sulfonamide was 74 mol%.

(1) Melting point: 266 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3400, 3340, 3240, 3160, 3060, 2970, 2940, 1635, 1584, 1522, 1460, 1408, 1226, 1160, 1092 1020, 862, 760, 662, 623.
(3) ¹ H-NMR (400 MHz, heavy acetone): δ = 0.82 (t, J = 8 Hz, 3H), 1.30-1.40 (m, 2H), 1.65-1.74 ( m, 2H), 1.75-1.78 (m, 1H), 2.20-2.25 (m, 1H), 2.50-2.57 (m, 1H), 2.86 (bs, 2H), 3.72 (t, J = 8H, 2H), 6.85 (s, 1H), 7.40-7.48 (m, 2H), 7.64 (d, J = 8 Hz, 1H) , 8.23 (d, J = 8 Hz, 1H).

(Synthesis Example 2) Synthesis of methylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide Synthesis was performed except that 930 mg of 40% methylamine aqueous solution (12 mmol as methylamine) was added instead of n-butylamine. The reaction was conducted in the same manner as in Example 1 to obtain 2.08 g of a white powder of methylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide. The isolation yield based on the raw material 1,4-naphthohydroquinone-2-sulfonamide was 77 mol%.

(1) Melting point: 250 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3360, 3250, 3180, 3080, 3035, 1630, 1578, 1510, 1452, 1400, 1308, 1225, 1202, 1186, 1084 1030, 1020, 904, 850, 772, 660, 572, 540.
(3) ¹ H-NMR (400 MHz, heavy acetone): δ = 1.72-1.76 (m, 1H), 2.19-2.25 (m, 1H), 2.48-2.54 ( m, 1H), 2.80 (bs, 2H), 3.38 (s, 3H), 6.84 (s, 1H), 7.40-7.46 (m, 2H), 7.63 (d , J = 8 Hz, 1H), 8.23 (d, J = 8 Hz, 1H).

(Synthesis Example 3) Synthesis of diethylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide As in Synthesis Example 1, except that 0.88 g (12 mmol) of diethylamine was added instead of n-butylamine. To obtain a white powder of 2.50 g of a diethylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide. The isolation yield based on the raw material 1,4-naphthohydroquinone-2-sulfonamide was 80 mol%.

(1) Melting point: 250 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3440, 3360, 3280, 3040, 2870, 2830, 1648, 1583, 1460, 1412, 1412, 1326, 1218, 1180, 1090, 1021,753,668,620,570.
(3) ¹ H-NMR (400 MHz, heavy acetone): δ = 1.33 (t, J = 8 Hz, 6H), 1.71-1.76 (m, 1H), 2.18-2.23 ( m, 1H), 2.88 (bs, 2H), 3.20 (q, J = 8 Hz, 4H), 6.83 (s, 1H), 7.42-7.48 (m, 1H), 7 .64 (d, J = 8 Hz, 1H), 8.24 (d, J = 8 Hz, 1H).

(Synthesis Example 4) Synthesis of 1,4-naphthohydroquinone-2-sulfonamide piperidine adduct As in Synthesis Example 1, except that 0.90 g (12 mmol) of piperidine was added instead of n-butylamine. To give 2.14 g of a white powder of piperidine adduct of 1,4-naphthohydroquinone-2-sulfonamide. The isolation yield based on the raw material 1,4-naphthohydroquinone-2-sulfonamide was 68 mol%.

(1) Melting point: 250 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3420, 3350, 3100, 3060, 2950, 2860, 1637, 1584, 1458, 1405, 1216, 1220, 1156, 1056, 1085, 1016 862, 772, 660, 618.
(3) ¹ H-NMR (400 MHz, heavy acetone): δ = 1.60-1.69 (m, 2H), 1.73-1.78 (m, 1H), 1.78-1.87 ( m, 4H), 2.20-2.26 (m, 1H), 2.92 (bs, 2H), 3.25-3.30 (m, 4H), 6.86 (s, 1H), 7 .42-7.49 (m, 2H), 7.65 (d, J = 8 Hz, 1H), 8.25 (d, J = 8 Hz, 1H).

(Synthesis Example 5) Synthesis of 1,4-naphthohydroquinone-2-sulfonamide triethylamine adduct As in Synthesis Example 1, except that 0.88 g (12 mmol) of triethylamine was added instead of n-butylamine. The reaction yielded 1.78 g (5.7 mmol) of white powder of triethylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide. The isolated yield based on the raw material 1,4-naphthohydroquinone-2-sulfonamide was 57 mol%.

(1) Melting point: 164-165 ° C
(2) IR (KBr, cm ⁻¹ ): 3445, 3360, 3260, 3200, 3020, 2800, 2720, 1640, 1460, 1400, 1236, 1220, 1174, 1138, 1084, 1032, 1003, 860, 772, 660, 620.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.29 (t, J = 8 Hz, 9H), 3.09 (t, J = 8 Hz, 6H), 3.83 (bs, 2H) 7.06 (s, 1H), 7.44-7.53 (m, 2H), 7.77 (d, J = 8 Hz, 1H), 8.32 (d.J = 8 Hz, 1H), 10 .22 (bs, 1H).

(Synthesis Example 6) Synthesis of tributylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide Synthetic Example 1 except that 2.22 g (12 mmol) of tributylamine was added instead of n-butylamine. The reaction was conducted in the same manner to obtain 3.8 g (9.0 mmol) of white powder of tributylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide. The isolation yield based on the raw material 1,4-naphthohydroquinone-2-sulfonamide was 90 mol%.

(1) Melting point: 112-113 ° C
(2) IR (KBr, cm ⁻¹ ): 3455, 3355, 3150, 3030, 2880, 1642, 1588, 1460, 1408, 1226, 1204, 1140, 1090, 1020, 860, 772, 716, 663, 622.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.88 (t, J = 8 Hz, 9H), 1.22-1.37 (m, 6H), 1.52-1.67 ( m, 6H), 2.91 (t, J = 8 Hz, 6H), 3.80 (bs, 2H), 7.07 (s, 1H), 7.47-7.56 (m, 2H), 7 .77 (d, J = 8 Hz, 1H), 8.32 (d, J = 8 Hz, 1H), 10.24 (bs, 1H).

Synthesis Example 7 Synthesis of 1,4-naphthohydroquinone-2-sulfonamide trioctylamine adduct Synthesis example except that 4.24 g (12 mmol) of trioctylamine was added instead of n-butylamine. In the same manner as in Example 1, a white powder of 3.26 g (5.5 mmol) of a trioctylamine adduct of 1,4-naphthohydroquinone-2-sulfonamide was obtained. The isolation yield based on the raw material 1,4-naphthohydroquinone-2-sulfonamide was 55 mol%.

(1) Melting point: 116-117 ° C
(2) IR (KBr, cm ⁻¹ ): 3450, 3340, 3140, 3050, 2970, 2940, 2870, 1640, 1590, 1460, 1408, 1380, 1325, 1228, 1208, 1148, 1090, 1020, 860, 760, 718, 664, 620.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.85 (t, J = 8 Hz, 9H), 1.08-1.30 (m, 30H), 1.55-1.68 ( m, 6H), 2.96 (t, J = 8 Hz, 6H), 3.79 (bs, 1H), 7.06 (s, 1H), 7.42-7.55 (m, 2H), 7 .76 (d, J = 8 Hz, 1H), 8.32 (d, J = 8 Hz, 1H), 9.80 (bs, 1H), 10.24 (s, 1H).

(Synthesis Example 8) Synthesis of DBU adduct of 1,4-naphthohydroquinone-2-sulfonamide 1,8-diazabicyclo- [5,4,0] -7-undecene (DBU) 1 instead of n-butylamine The reaction was conducted in the same manner as in Synthesis Example 1 except that .82 g (12 mmol) was added, and 3.6 g (9.2 mmol) of a white powder of DBU adduct of 1,4-naphthohydroquinone-2-sulfonamide Got. The isolated yield based on the raw material 1,4-naphthohydroquinone-2-sulfonamide was 92 mol%.

(1) Melting point: 185-186 ° C
(2) IR (KBr, cm ⁻¹ ): 3440, 3360, 3270, 3140, 2840, 1655, 1460, 1402, 1326, 1230, 1206, 1162, 1150, 1088, 1020, 860, 770, 717, 660, 620.
(3) ¹ H-NMR (400 MHz, heavy acetone): δ = 1.63-1.78 (m, 6H), 3.40 (t, J = 8 Hz, 2H), 3.58-3.69 ( m, 4H), 4.50 (s, 1H), 7.00 (s, 1H), 7.35-7.43 (m, 2H), 7.91 (d, J = 8 Hz, 1H), 8 .20 (d, J = 8 Hz, 1H), 11.09 (s, 1H).

(Evaluation Example 1)
10 mg of Irgacure 184 (manufactured by 1-hydroxycyclohexyl phenyl ketone BSF, Irgacure is a registered trademark of BSF) as a photopolymerization initiator was added to 2 g of trimethylolpropane triacrylate, and the same method as in Synthesis Example 7 was added thereto. 2 mg of the obtained 1,4-naphthohydroquinonesulfonamide trioctylamine adduct was added to obtain a uniform liquid composition. This was put in a 10 ml sample tube and irradiated with light using a 365 nm light source (irradiation intensity: 4 mW / cm ² ) in a nitrogen atmosphere. Although the composition was irradiated with light for 3 minutes, the composition remained liquid.

(Evaluation Example 2)
Evaluation Example 1 except that the trioctylamine adduct of 1,4-naphthohydroquinonesulfonamide was replaced with the tributylamine adduct of 1,4-naphthohydroquinonesulfonamide obtained in the same manner as in Synthesis Example 6. A liquid composition was prepared exactly as described above. This was put in a 10 ml sample tube and irradiated with light using a 365 nm light source (irradiation intensity: 4 mW / cm ² ) in a nitrogen atmosphere. Although the composition was irradiated with light for 3 minutes, the composition remained liquid.

(Evaluation Example 3)
Evaluation Example 1 except that the trioctylamine adduct of 1,4-naphthohydroquinonesulfonamide was replaced with the triethylamine adduct of 1,4-naphthohydroquinonesulfonamide obtained in the same manner as in Synthesis Example 5. A liquid composition was prepared in exactly the same manner. This was put in a 10 ml sample tube and irradiated with light using a 365 nm light source (irradiation intensity: 4 mW / cm ² ) in a nitrogen atmosphere. Although the composition was irradiated with light for 3 minutes, the composition remained liquid.

(Evaluation Example 4)
Evaluation Example 1 except that the trioctylamine adduct of 1,4-naphthohydroquinonesulfonamide was replaced with the diethylamine adduct of 1,4-naphthohydroquinonesulfonamide obtained in the same manner as in Synthesis Example 3. A liquid composition was prepared in exactly the same manner. This was put in a 10 ml sample tube and irradiated with light using a 365 nm light source (irradiation intensity: 4 mW / cm ² ) in a nitrogen atmosphere. Although the composition was irradiated with light for 3 minutes, the composition remained liquid.

(Evaluation Example 5)
Evaluation Example 1 except that the trioctylamine adduct of 1,4-naphthohydroquinonesulfonamide was replaced with the piperidine adduct of 1,4-naphthohydroquinonesulfonamide obtained in the same manner as in Synthesis Example 4. A liquid composition was prepared in exactly the same manner. This was put in a 10 ml sample tube and irradiated with light using a 365 nm light source (irradiation intensity: 4 mW / cm ² ) in a nitrogen atmosphere. Although the composition was irradiated with light for 3 minutes, the composition remained liquid.

(Evaluation Example 6)
Evaluation Example 1 except that the trioctylamine adduct of 1,4-naphthohydroquinonesulfonamide was replaced with the butylamine adduct of 1,4-naphthohydroquinonesulfonamide obtained in the same manner as in Synthesis Example 1. A liquid composition was prepared in exactly the same manner. This was put in a 10 ml sample tube and irradiated with light using a 365 nm light source (irradiation intensity: 4 mW / cm ² ) in a nitrogen atmosphere. Although the composition was irradiated with light for 3 minutes, the composition remained liquid.

(Evaluation Comparative Example 1)
A liquid composition was prepared in the same manner as in Evaluation Example 1, except that the trioctylamine adduct of 1,4-naphthohydroquinonesulfonamide was not added, and this was put in a 10 ml sample tube and a nitrogen atmosphere. The light was irradiated using a 365 nm light source (irradiation intensity: 4 mW / cm ² ). After 30 seconds, the composition was completely cured.

(Evaluation Comparative Example 2)
A liquid composition in the same manner as in Evaluation Example 1 except that the trioctylamine adduct of 1,4-naphthohydroquinonesulfonamide was changed to 1,4-naphthohydroquinonesulfonamide obtained by the same method as in Synthesis Example 1. A product was prepared, placed in a 10 ml sample tube, and irradiated with light using a 365 nm light source (irradiation intensity: 4 mW / cm ² ) in a nitrogen atmosphere. After 30 seconds, the composition was completely cured.

(Evaluation Comparative Example 3)
A liquid composition was prepared in the same manner as in Evaluation Example 1 except that the trioctylamine adduct of 1,4-naphthohydroquinonesulfonamide was replaced with 1,4-naphthohydroquinone. And irradiated with light using a 365 nm light source (irradiation intensity: 4 mW / cm ² ) in a nitrogen atmosphere. The composition was completely cured after 2 minutes.

The following is clear from the results of the above Evaluation Examples 1 to 6 and Evaluation Comparative Examples 1 to 3. That is, the amine adduct of 1,4-naphthohydroquinonesulfonamide of the present invention has a polymerization inhibitory effect on trimethylolpropane triacrylate which is a vinyl monomer, and 1,4-naphthohydroquinonesulfonamide as a polymerization inhibitor. Compared to the naphthalene-based polymerization inhibitor 1,4-naphthohydroquinone known so far, it can be seen that the polymerization inhibition performance is high.

Claims (8)

An amine adduct of 1,4-naphthohydroquinone-2-sulfonamide represented by the following general formula (1).

(In general formula (1), amine represents a primary amine compound, a secondary amine compound, a tertiary amine compound, an amidine compound or a guanidine compound, and n represents 1 or 2.) The amine adduct of 1,4-naphthohydroquinone-2-sulfonamide according to claim 1, wherein the amine is a tertiary amine compound or an amidine compound. Amine addition of 1,4-naphthohydroquinone-2-sulfonamide according to claim 1 or 2, by reacting 1,4-naphthohydroquinone-2-sulfonamide represented by the following structural formula (2) with an amine. Manufacturing method.
A polymerization inhibitor comprising the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide according to claim 1 or 2. A vinyl monomer composition comprising a polymerization inhibitor containing a vinyl monomer and an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide according to claim 4.   The vinyl monomer composition according to claim 5, wherein the vinyl monomer is an α, β-unsaturated carboxylic acid compound, an α, β-unsaturated carboxylic acid ester compound or an aromatic vinyl compound. A method for inhibiting polymerization of a vinyl monomer, comprising using a polymerization inhibitor containing the amine adduct of 1,4-naphthohydroquinone-2-sulfonamide according to claim 4. The method for inhibiting polymerization of a vinyl monomer according to claim 7, wherein the amount of the polymerization inhibitor containing an amine adduct of 1,4-naphthohydroquinone-2-sulfonamide is 1 ppm or more and 1000 ppm or less with respect to the vinyl monomer.