JP7228877B2 - Method for producing polymerizable vinyl compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polymerizable vinyl compound. More specifically, production of a polymerizable vinyl compound capable of suppressing the polymerization of a specific polymerizable vinyl compound when purifying the polymerizable vinyl compound by distillation and producing the polymerizable vinyl compound with high productivity. Regarding the method.

In recent years, the use of vinyl monomers (polymerizable vinyl compounds) has been expanding, and along with this, various vinyl monomers have been proposed for the purpose of imparting various functions. New vinyl monomers developed in such technological development tend to have higher molecular weights or higher boiling points due to the addition of substituents.

Here, in many cases, vinyl monomers are purified by distillation after production for economic reasons. The heat during this distillation may cause the vinyl monomer to polymerize, and once polymerized, the distillation becomes difficult. In order to prevent such problems, a polymerization inhibitor is added during distillation of the vinyl monomer.

On the other hand, as the boiling point of the vinyl monomer increases as described above, the distillation temperature rises and the degree of pressure reduction during distillation decreases, so that the added polymerization inhibitor distills out together with the vinyl monomer during distillation. However, there is a problem that the polymerization inhibitor is entrained with the vinyl monomer during distillation.

In order to address such problems, polymerization inhibitors that are less likely to accompany vinyl monomers during distillation have been proposed (see Patent Documents 1 and 2).

Here, N-oxyl compounds are known to be effective polymerization inhibitors used in the production of vinyl monomers. As for this N-oxyl compound, as the boiling point of the vinyl monomer increases, a substance (polymerization inhibitor) that is difficult to accompany the vinyl monomer has been proposed. , there is a problem that the polymerization in the gas phase portion of the distillation apparatus cannot be efficiently prevented.

In response to such problems, Japanese Patent Application Laid-Open No. 56-38301 (Patent Document 3) describes two types of N-oxyls having different vaporization temperatures during distillation of α,β-unsaturated carboxylic acid esters. A technique using a compound (polymerization inhibitor) in combination is described.

JP 2016-199632 A Japanese Patent Application Laid-Open No. 2017-110160 JP-A-56-38301 Japanese Patent No. 6282353

However, although Cited Document 3 describes α,β-unsaturated carboxylic acid esters and Cited Document 4 describes (meth)acrylate compounds, polymerizable vinyl compounds other than these have high boiling points. No technology has yet been developed to simultaneously prevent the entrainment of the vinyl monomer and the polymerization inhibitor during the distillation of the resulting product and prevent the polymerization of the vinyl monomer in the gas phase of the distillation apparatus. not

The present invention has been made in view of such problems of the prior art. In the method for producing a polymerizable vinyl compound of the present invention, when a specific polymerizable vinyl compound (that is, a polymerizable vinyl compound excluding (meth)acrylate compounds) is purified by distillation, the polymerizable vinyl compound is polymerized (especially by distillation). Polymerization in the gas phase of the apparatus) can be suppressed, and a polymerizable vinyl compound can be produced with high productivity.

According to the present invention, the following method for producing a polymerizable vinyl compound is provided.

[1] At least one N- an oxyl compound, and at least one N selected from the following group B consisting of (B-1) to (B-6), which is a compound having a boiling point higher than that of the N-oxyl compound selected from group A - After obtaining a distillation stock solution by adding an oxyl compound, the distillation stock is distilled at a high boiling point of 150 ° C. or higher for 4 hours or more to obtain a polymerizable vinyl compound contained in the distillation stock solution, polymerizable A method for producing a vinyl compound.

[2] The method for producing a polymerizable vinyl compound according to [1], wherein the polymerizable vinyl compound in the raw material liquid is a conjugated diene compound.

[3] The method for producing a polymerizable vinyl compound according to [1], wherein the polymerizable vinyl compound in the raw material liquid is a vinyl ester compound.

[4] The method for producing a polymerizable vinyl compound according to [1] above, wherein the polymerizable vinyl compound in the raw material liquid is an aromatic vinyl compound.

[5] The addition amount of at least one N-oxyl compound selected from the group A is 1 ppm or more with respect to the mass of the distillation stock solution,
The polymerizability according to any one of [1] to [4], wherein the addition amount of at least one N-oxyl compound selected from the group B is 10 ppm or more with respect to the mass of the stock solution for distillation. A method for producing a vinyl compound.

[6] Formula: The value of the added amount of at least one N-oxyl compound selected from Group A/the added amount of at least one N-oxyl compound selected from Group B is 0.001 to 1. The method for producing a polymerizable vinyl compound according to any one of [1] to [5] above.

The method for producing a polymerizable vinyl compound of the present invention suppresses polymerization of a specific polymerizable vinyl compound (that is, a polymerizable vinyl compound excluding a (meth)acrylate compound) during purification by distillation. The effect is that the polymerizable vinyl compound can be produced with high productivity.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments for carrying out the present invention will be described below, but the present invention is not limited to the following embodiments. In other words, it is understood that any modifications, improvements, etc., made to the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention also belong to the scope of the present invention. should.

(1) Method for producing a polymerizable vinyl compound:
In the method for producing a polymerizable vinyl compound of the present invention, the following (A-1 ) to (A-4), and at least one N-oxyl compound selected from Group A, and a compound having a higher boiling point than the N-oxyl compound selected from Group A, and the following (B- 1) After adding at least one N-oxyl compound selected from the group B consisting of to (B-6) to obtain a distillation stock solution (distillation stock solution preparation step), the distillation raw material was heated to 150 ° C. or higher . to obtain the polymerizable vinyl compound contained in the stock solution for distillation (obtain a purified polymerizable vinyl compound-containing liquid) (distillation purification step). In addition, when a plurality of N-oxyl compounds are selected from Group A, the one with the highest boiling point among the selected compounds is used as a standard, and from Group B, the boiling point is higher than the boiling point of the standard compound. The higher one shall be selected.

According to such a method for producing a polymerizable vinyl compound, when purifying a specific polymerizable vinyl compound (that is, a polymerizable vinyl compound excluding a (meth)acrylate compound) by distillation, polymerization of the polymerizable vinyl compound is performed. can be suppressed, and the polymerizable vinyl compound can be produced with good productivity.

(1-1) Distillation stock solution preparation step:
Specific examples of polymerizable vinyl compounds (excluding (meth)acrylate compounds) include conjugated diene compounds, vinyl ester compounds, and aromatic vinyl compounds. More specifically, the polymerizable vinyl compound (excluding (meth)acrylate compounds) is preferably a conjugated diene compound, a vinyl ester compound, or an aromatic vinyl compound.

Examples of conjugated diene compounds include butadiene, isoprene, farnesene, myrcene, chloroprene, 2,3-dimethylbutadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3- -hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, α-farnesene, β-farnesene, myrcene, chloroprene, and the like. be able to.

Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, and the like.

Examples of aromatic vinyl compounds include styrene, vinyltoluene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene and 4-dodecylstyrene. , 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene , vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, styrenesulfonic acid, and divinylbenzene.

Examples of polymerizable vinyl compounds other than conjugated diene compounds, vinyl ester compounds, and aromatic vinyl compounds include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, and cyclohexyl acrylate. , heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, benzyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, acrylic acid -2-hydroxypropyl, stearyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, trifluoromethylmethyl acrylate, 2-perfluoroethylethyl acrylate, isobornyl acrylate, adamantyl acrylate, bicyclohexyl acrylate, etc. , acrylic acid derivatives, and the like.

Further, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, methacryl phenyl acid, benzyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, methacrylic acid 2 methacrylic acid derivatives such as -aminoethyl, trifluoromethylmethyl methacrylate, 2-perfluoroethylethyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, and bicyclohexyl methacrylate.

Furthermore, fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride, and vinyl group-containing silanes such as vinyltrimethoxysilane and vinyltriethoxysilane can be used.

In addition, maleic anhydride, maleic acid, monoalkyl esters of maleic acid, dialkyl esters, fumaric acid, monoalkyl esters of fumaric acid, dialkyl esters, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octyl Maleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like can be mentioned.

Furthermore, acrylonitrile-based monomers such as acrylonitrile and methacrylonitrile can be used.

Furthermore, amide group-containing vinyl monomers such as acrylamide and methacrylamide can be used.

Furthermore, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like can be mentioned.

The distillation raw material includes at least one N-oxyl compound selected from Group A consisting of (A-1) to (A-4) above, and a boiling point higher than that of the N-oxyl compound selected from Group A. and at least one N-oxyl compound selected from Group B consisting of the above (B-1) to (B-6). The combination of these two types of polymerization inhibitors is not particularly limited, and multiple compounds from each group may be employed. Among these combinations, for example, by combining the N-oxyl compound (A-1) and the N-oxyl compound (B-6), a conjugated diene compound, a vinyl ester compound, or an aromatic vinyl compound is produced. A more excellent effect of inhibiting polymerization is obtained.

In addition to the polymerizable vinyl compound (excluding (meth)acrylate compounds), the raw material liquid includes a solvent for the polymerizable vinyl compound, a by-product (contaminant) generated during the synthesis of the polymerizable vinyl compound, and the like. include.

In the present invention, the amount of at least one N-oxyl compound selected from Group A to be added is preferably 1 ppm or more, more preferably 10 to 10000 ppm, relative to the mass of the stock solution for distillation. The amount of at least one N-oxyl compound selected from Group B to be added is preferably 10 ppm or more, more preferably 100 to 10000 ppm, relative to the mass of the stock solution for distillation. Thus, the addition amount of at least one N-oxyl compound selected from group A and the addition amount of at least one N-oxyl compound selected from group B are within the above ranges, whereby polymerization A more excellent polymerization inhibition effect is exerted against the polymerization of the vinyl compound during distillation.

In the present invention, the value of the formula: addition amount (ppm) of at least one N-oxyl compound selected from group A/addition amount (ppm) of at least one N-oxyl compound selected from group B is It is preferably from 0.001 to 1, more preferably from 0.01 to 1. When the above value is within the above range, a further excellent polymerization inhibition effect is exhibited against the polymerization of polymerizable vinyl compounds (especially conjugated diene compounds, vinyl ester compounds, and aromatic vinyl compounds) during distillation. be done.

Incidentally, "the added amount of at least one N-oxyl compound selected from Group A" refers to the total added amount of at least one N-oxyl compound selected from Group A when there are multiple N-oxyl compounds. . In addition, "the added amount of at least one N-oxyl compound selected from the above group B" refers to the total added amount of at least one N-oxyl compound selected from the B group when there is more than one. say.

(1-2) Distillation purification step:
As the distillation conditions, conventionally known conditions can be appropriately selected. For example, distillation is performed at a temperature of 190° C. for 10 hours.

EXAMPLES The present invention will be specifically described below based on Examples, but the present invention is not limited to these Examples.

(Example 1)
Using a glass simple distillation apparatus, styrene, 5000 ppm of 4H-TEMPO and 5000 ppm of 4-benzoyloxy TEMPO were added to the simple distillation apparatus to distill styrene. The styrene used was previously washed with a 10% NaOH aqueous solution to remove the stabilizer.

Distillation was carried out for 10 hours under normal pressure in a nitrogen stream at a temperature of 150° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. The washing liquid was transparent, and it was determined that no polymer of styrene was produced (polymerization of styrene was inhibited).

(Comparative example 1)
Using a glass simple distillation apparatus, styrene and 10000 ppm of 4-benzoyloxy TEMPO were added to the simple distillation apparatus to distill styrene. The styrene used was previously washed with a 10% NaOH aqueous solution to remove the stabilizer.

Distillation was carried out for 10 hours under normal pressure in a nitrogen stream at a temperature of 150° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. White turbidity was observed in the washing liquid. From this result, it was determined that a polymer of styrene was generated in the air layer (polymerization of styrene was not sufficiently suppressed).

(Example 4)
Using a glass simple distillation apparatus, styrene, 1000 ppm of 4H-TEMPO and 1000 ppm of 4-benzoyloxy TEMPO were added to the simple distillation apparatus to distill styrene. The styrene used was previously washed with a 10% NaOH aqueous solution to remove the stabilizer.

Distillation was carried out for 4 hours under normal pressure in a nitrogen stream at a temperature of 150° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. The washing liquid was transparent, and it was determined that no polymer of styrene was produced (polymerization of styrene was inhibited).

(Comparative Example 4)
Using a glass simple distillation apparatus, styrene and 2000 ppm of 4-benzoyloxy TEMPO were added to the simple distillation apparatus to distill styrene. The styrene used was previously washed with a 10% NaOH aqueous solution to remove the stabilizer.

Distillation was carried out for 4 hours under normal pressure in a nitrogen stream at a temperature of 150° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. White turbidity was observed in the washing liquid. From this result, it was determined that a polymer of styrene was generated in the air layer (polymerization of styrene was not sufficiently suppressed).

(Example 2)
Using a glass single distillation apparatus, vinyl 2-ethylhexanoate (vinyl ester compound), 4H-TEMPO 5000 ppm, BisTEMPO sebacate (bis(2,2,6,6-tetramethyl-1 -piperazinyloxy-4-yl)sebacate) 5000 ppm was added and distillation of vinyl 2-ethylhexanoate was carried out. (Vinyl 2-ethylhexanoate was used after washing with a 10% NaOH aqueous solution to remove the stabilizer.

Distillation was carried out for 10 hours under normal pressure in a nitrogen stream at a temperature of 190° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. The washing liquid was transparent, and it was determined that no polymer of vinyl 2-ethylhexanoate was formed (polymerization of vinyl 2-ethylhexanoate was suppressed).

(Comparative example 2)
Using a glass simple distillation apparatus, vinyl 2-ethylhexanoate and BisTEMPO sebacate (bis(2,2,6,6-tetramethyl-1-piperazinyloxy-4-yl)) were added to the simple distillation apparatus. Sebacate) was added at 10000 ppm, and vinyl 2-ethylhexanoate was distilled. The vinyl 2-ethylhexanoate used was previously washed with a 10% NaOH aqueous solution to remove the stabilizer.

(Example 5)
Using a glass single distillation apparatus, vinyl 2-ethylhexanoate (vinyl ester compound), 4H-TEMPO 1000 ppm, BisTEMPO sebacate (bis(2,2,6,6-tetramethyl-1 -piperazinyloxy-4-yl)sebacate) 1000 ppm was added and distillation of vinyl 2-ethylhexanoate was carried out. (Vinyl 2-ethylhexanoate was used after washing with a 10% NaOH aqueous solution to remove the stabilizer.

Distillation was carried out for 4 hours under normal pressure in a nitrogen stream at a temperature of 190° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. The washing liquid was transparent, and it was determined that no polymer of vinyl 2-ethylhexanoate was formed (polymerization of vinyl 2-ethylhexanoate was suppressed).

(Comparative Example 5)
Using a glass simple distillation apparatus, vinyl 2-ethylhexanoate and BisTEMPO sebacate (bis(2,2,6,6-tetramethyl-1-piperazinyloxy-4-yl)) were added to the simple distillation apparatus. Sebacate) was added at 2000 ppm, and vinyl 2-ethylhexanoate was distilled. The vinyl 2-ethylhexanoate used was previously washed with a 10% NaOH aqueous solution to remove the stabilizer.

Distillation was carried out for 4 hours under normal pressure in a nitrogen stream at a temperature of 190° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. White turbidity was observed in the washing liquid. From this result, it was determined that a polymer of vinyl 2-ethylhexanoate was formed in the gas layer (polymerization of vinyl 2-ethylhexanoate was not sufficiently inhibited).

(Example 3)
Using a glass simple distillation apparatus, myrcene, 5000 ppm of 4H-TEMPO and 5000 ppm of 4-benzoyloxy TEMPO were added to the simple distillation apparatus to distill myrcene. Distillation was carried out for 10 hours under normal pressure in a nitrogen stream at a temperature of 180° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. The washing liquid was transparent, and it was judged that no polymerization product of myrcene was produced (polymerization of myrcene was suppressed).

(Comparative Example 3)
Using a glass-made simple distillation apparatus, myrcene and 10000 ppm of 4-benzoyloxy TEMPO were added to the simple distillation apparatus to distill myrcene. Distillation was carried out for 10 hours under normal pressure in a nitrogen stream at a temperature of 190° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. White turbidity was observed in the washing liquid. From this result, it was determined that a polymer of myrcene was formed in the gas layer (polymerization of myrcene was not sufficiently suppressed).

(Example 6)
Using a glass simple distillation apparatus, myrcene, 1000 ppm of 4H-TEMPO and 1000 ppm of 4-benzoyloxy TEMPO were added to the simple distillation apparatus to distill myrcene. Distillation was carried out for 4 hours under normal pressure in a nitrogen stream at a temperature of 180° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. The washing liquid was transparent, and it was judged that no polymerization product of myrcene was produced (polymerization of myrcene was suppressed).

(Comparative Example 6)
Using a glass simple distillation apparatus, myrcene and 2000 ppm of 4-benzoyloxy TEMPO were added to the simple distillation apparatus to distill myrcene. Distillation was carried out for 4 hours under normal pressure in a nitrogen stream at a temperature of 190° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. White turbidity was observed in the washing liquid. From this result, it was determined that a polymer of myrcene was formed in the gas layer (polymerization of myrcene was not sufficiently suppressed).

(Comparative Example 7)
Using a glass-made simple distillation apparatus, 2-ethoxyethyl methacrylate, 4H-TEMPO 5000 ppm, and BisTEMPO sebacate (bis(2,2,6,6-tetramethyl-1-piperazinyloxy -4-yl) sebacate) 5000 ppm was added and distilled. The 2-ethoxyethyl methacrylate used was previously washed with a 10% NaOH aqueous solution to remove the stabilizer.

Distillation was carried out under a nitrogen stream at normal pressure and at an oil bath temperature of 190°C.

(Example 7)
Using a glass simple distillation apparatus, myrcene, 4H-TEMPO 5000 ppm, and BisTEMPO sebacate (bis (2,2,6,6-tetramethyl-1-piperazinyloxy-4-yl)) were added to the simple distillation apparatus. Sebacate) was added at 5000 ppm, and myrcene was distilled. Distillation was carried out for 10 hours under normal pressure in a nitrogen stream at a temperature of 180° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. The washing liquid was transparent, and it was judged that no polymerization product of myrcene was produced (polymerization of myrcene was suppressed).

(Comparative Example 8)
Myrcene and BisTEMPO sebacate (bis(2,2,6,6-tetramethyl-1-piperazinyloxy-4-yl) sebacate) 10000 ppm were added to the simple distillation apparatus using a glass simple distillation apparatus. , for the distillation of myrcene. Distillation was carried out for 10 hours under normal pressure in a nitrogen stream at a temperature of 190° C. in an oil bath, and then the gas layer of the simple distillation apparatus was washed with methanol. At that time, the state of the washing liquid was confirmed. White turbidity was observed in the washing liquid. From this result, it was determined that a polymer of myrcene was formed in the gas layer (polymerization of myrcene was not sufficiently suppressed).

Table 1 shows the results of Examples 1 to 7 and Comparative Examples 1 to 8. Note that the hatched lines in the column of "state of washing liquid" in Comparative Example 7 mean that the state of washing liquid could not be confirmed. Specifically, 2-ethoxyethyl methacrylate polymerized in the test liquid in the simple distillation apparatus (that is, the polymerization of 2-ethoxyethyl methacrylate was not suppressed), and the evaluation test could not be performed. show.

As described above, according to the production methods of the polymerizable vinyl compounds of Examples 1 to 7, the polymerization of the polymerizable vinyl compounds can be sufficiently suppressed during distillation, while the polymerization of the polymerizable vinyl compounds of Comparative Examples 1 to 8 can be sufficiently suppressed. In the method for producing a vinyl compound, the polymerization of the polymerizable vinyl compound could not be sufficiently suppressed during distillation.

The method for producing a polymerizable vinyl compound of the present invention can produce a polymerizable vinyl compound while inhibiting polymerization of the polymerizable vinyl compound (excluding (meth)acrylate compounds) during distillation of the polymerizable vinyl compound such as styrene. can be adopted as a method.

Claims (6)

At least one N-oxyl compound selected from Group A consisting of (A-1) to (A-4) below is added to a raw material solution containing a polymerizable vinyl compound (excluding (meth)acrylate compounds), and at least one N-oxyl compound selected from Group B consisting of (B-1) to (B-6) below, which has a higher boiling point than the N-oxyl compound selected from Group A. is added to obtain a distillation stock solution, and then the distillation stock is distilled at a high boiling point of 150 ° C. or higher for 4 hours or more to obtain a polymerizable vinyl compound contained in the distillation stock solution. Production method.

2. The method for producing a polymerizable vinyl compound according to claim 1, wherein the polymerizable vinyl compound in the raw material liquid is a conjugated diene compound. 2. The method for producing a polymerizable vinyl compound according to claim 1, wherein the polymerizable vinyl compound in the raw material liquid is a vinyl ester compound. 2. The method for producing a polymerizable vinyl compound according to claim 1, wherein the polymerizable vinyl compound in the raw material liquid is an aromatic vinyl compound. The addition amount of at least one N-oxyl compound selected from the group A is 1 ppm or more with respect to the mass of the distillation stock solution,
The polymerizable vinyl according to any one of claims 1 to 4, wherein the added amount of at least one N-oxyl compound selected from group B is 10 ppm or more with respect to the mass of the stock solution for distillation. A method for producing a compound. Formula: The value of the added amount of at least one N-oxyl compound selected from Group A/the added amount of at least one N-oxyl compound selected from Group B is 0.001 to 1. Item 6. A method for producing the polymerizable vinyl compound according to any one of Items 1 to 5.