JP2003040825A - Method for distilling styrene or styrene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for distilling styrene or a styrene derivative in which conventional disadvantages are eliminated. SOLUTION: This method for distilling styrene or the styrene derivative comprises by adding 1,2,4-benzenetriol or its derivative as a polymerization inhibitor to styrene or the styrene derivative represented by following formula (II) (wherein, Ys denote each an alkyl group, a haloalkyl group, an aryl group, an arylalkyl group, an alkoxyalkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an arylalkoxycarbonyl group or an alkylsilyl group) and distilling styrene or the styrene derivative in the presence of the polymerization inhibitor. The method provides prevention of formation of highly viscous polymeric substances in a distillation step and a high recovery ratio of the distilled styrene or styrene derivative.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for distilling styrene or a styrene derivative, which is useful as a raw material for medical and agricultural chemicals or functional polymers, polymer synthesis, etc., for the purpose of purification after its synthesis.

[0002]

2. Description of the Related Art Among styrene derivatives, for example, p-tert.
-Butoxystyrene (hereinafter abbreviated as "PTBST". "PTBST" is a registered trademark of the applicant) is known to be extremely useful as a resist raw material used in VLSI applications and the like. JP-A-59-199705, JP-A-3-277608, and m-tert-butoxystyrene (hereinafter referred to as "MTB").
Abbreviated as "ST". Is known to be useful as an intermediate raw material for functional polymers, pharmaceuticals, agricultural chemicals, etc. (Japanese Patent Laid-Open No. 2-1
60739 publication).

The following methods are known as methods for synthesizing styrene derivatives. For example, styrene derivatives such as 4-chlorostyrene, 3,4-dichlorostyrene, α-methyl-3-chlorostyrene, 4-trifluoromethylstyrene, 4-methylstyrene and 4-methoxystyrene are the corresponding N-acyl A method (Japanese Patent Laid-Open No. 61-212526) obtained by treating -β-phenethylamines with a base is known. 4-acetoxystyrene, 4-
It is known that styrene derivatives such as trimethylsilyloxystyrene can be obtained by reacting a corresponding substituted benzaldehyde with dibromomethane (Japanese Patent Laid-Open No. 08-157410). Furthermore, tert-butoxystyrene such as PTBST and MTBST is chlorostyrene, bromostyrene,
A method is known in which a Grignard reagent is prepared from halogen-substituted styrene such as iodostyrene and magnesium and then reacted with tert-butyl perbenzoate to synthesize the compound (Japanese Patent Laid-Open No. 59-199705).

Further, a Grignard reagent is prepared from tert-butoxyphenyl halide such as tert-butoxyphenyl chloride, tert-butoxyphenyl bromide, tert-butoxyphenyl iodide and magnesium, and then the Grignard reagent is vinyl chloride or vinyl bromide. A method of synthesizing by coupling with vinyl halide such as JP-A-4-71896, JP-A-2-16073
No. 9) is known.

In the method for synthesizing the styrene derivative as described above, the synthesized target styrene derivative is usually separated and purified by distillation. However, since the styrene derivative is generally polymerized by light or heat to form a highly viscous liquid polymeric substance, the product recovery rate during distillation may be significantly reduced. Furthermore, in the distillation column, in the distillation can, piping, etc. due to the generated polymeric substance,
Blocking of the distillation column or piping, abnormal pressure reduction due to the above,
This may cause troubles such as difficulty in cleaning due to adhesion of the polymeric substance. Therefore, in order to avoid these troubles, it has been customary to add various polymerization inhibitors to the styrene derivative and carry out the distillation operation in the presence thereof. As the method, for example,
In the distillation of tert-butoxystyrene such as PTBST and MTBST, a method of performing distillation in the presence of 4-tert-butylcatechol (Japanese Examined Patent Publication No. 4-71896, JP-A No. 2-160739) and N-nitroso A method of distilling in the presence of phenylhydroxylamine aluminum salt, N-nitrosophenylhydroxylamine ammonium salt, 2,4-dinitrophenol or the like (JP-A-2000-327617) is disclosed.

However, the above-mentioned conventionally used polymerization inhibitors do not exhibit a sufficient inhibitory effect on the formation of a polymeric substance under the severe conditions of long time and high temperature in the distillation step of the styrene derivative, so that they have high viscosity. A viscous polymeric substance is formed, blockage of the distillation column or pipe in the distillation column or distillation can, abnormal pressure reduction due to the above,
It often causes troubles such as difficulty in cleaning due to adhesion of the polymeric substance. Further, even if trouble does not occur, there is always a problem that the yield of the product after distillation is reduced. For these reasons, conventional distillation methods for styrene derivatives have not been satisfactory.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new distillation method for styrene or styrene derivatives which can overcome the drawbacks of the conventional methods. In other words, there is almost no formation of polymeric substance that occurs in the conventional method,
In addition, styrene, 4-chlorostyrene, 3,4-dichlorostyrene, α-methyl-3-chlorostyrene, 4-trifluoromethylstyrene, 4-methylstyrene can be obtained with a high product recovery rate even by distillation operation for a long time. The present invention is to provide a novel distillation method capable of purifying styrene derivatives such as 4-methoxystyrene, 4-acetoxystyrene, 4-trimethylsilyloxystyrene, PTBST and MTBST by distillation.

[0008]

[Means for Solving the Problems] The present inventors have conducted intensive studies in order to solve the conventional problems. As a result, in the distillation step of styrene or styrene derivative, by adding 1,2,4-benzenetriol or its derivative as a polymerization inhibitor and distilling in the presence thereof,
It has been found that styrene or styrene derivatives can be distilled with high recovery without the formation of polymeric substances. The present invention has been completed based on this finding.

Therefore, in the present invention, 1, 2, 4
Provided is a method for distilling styrene or a styrene derivative, which comprises adding benzenetriol or a derivative thereof as a polymerization inhibitor to styrene or a styrene derivative, and distilling the styrene or the styrene derivative in the presence of the polymerization inhibitor. To be done.

The method of the present invention will be described in detail below. The styrene or styrene derivative distilled in the present invention is a known compound and can be synthesized by a known synthesis method (for example, Japanese Patent Publication No. 4-71896).

The styrene or styrene derivative distilled in the method of the present invention has the following general formula (II): (In the formula, Y is a hydrogen atom, an amino group, an alkyl group, an alkenyl group, an alkynyl group, a halogen atom, a haloalkyl group, an aryl group, particularly a phenyl group, an aralkyl group, particularly a benzyl group, an alkoxyalkyl group, a nitro group, an alkanoyl group. , Especially acetyl group, aroyl group, especially benzoyl group, alkoxycarbonyl group, arylalkoxycarbonyl group, alkoxy group, haloalkoxy group, aryloxy group, aralkyloxy group, alkoxyalkyloxy group, alkanoyloxy group, alkoxycarbonyloxy group, Represents an aralkyloxycarbonyloxy group, or an alkylsilyloxy group, n is 0 or an integer from 1 to 4, and when n is 2 or more, Y represents the same or different n groups. may indicate further X ^1, X ^2, X ^3, it Independently, a hydrogen atom, an alkyl group, can be an alkoxy group, a halogen atom, a compound represented by an alkyl silyl group or a nitro group). The styrene derivative is particularly represented by the following general formula (IIa) (In the formula, Z is an alkyl group, a haloalkyl group, an aryl group, particularly a phenyl group, an aralkyl group, especially a benzyl group,
An alkoxyalkyl group, an alkanoyl group, particularly an acetyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group, and further X ¹ ,
X ² and X ³ are each independently a hydrogen atom, an alkyl group,
An oxystyrene derivative represented by an alkoxy group, a halogen atom, an alkylsilyloxy group or a nitro group, and n is an integer of 1 to 4, and more preferably the following general formula (IIb) (In the formula, Z'is an alkyl group, a haloalkyl group, an aryl group, particularly a phenyl group, an aralkyl group, especially a benzyl group,
An oxystyrene derivative represented by an alkoxyalkyl group, an alkanoyl group, particularly an acetyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group).

Specific examples of the styrene or styrene derivative represented by the general formula (II), (IIa) or (IIb) include the following. That is, styrene, p-aminostyrene, p-methylstyrene, p-ethylstyrene, p-n-propylstyrene, p-iso-propylstyrene, p-n-butylstyrene, p-iso-butylstyrene, p-sec. -Butylstyrene, p-tert-butylstyrene, p-n-amylstyrene, p-iso-amylstyrene, p-sec-amylstyrene, p-tert-amylstyrene, p-cyclopropylstyrene, p-cyclopropylmethyl Styrene, p-cyclopentylstyrene, p-cyclohexylstyrene, p-vinylstyrene, p-allylstyrene, p-ethynylstyrene, p-propargylstyrene, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-iodo. Styrene, p-chloromethylstyrene, p-bromomethylstyrene, p-iodomethylstyrene, p-trifluorome Cylstyrene, p-phenylstyrene, p- (4-methylphenyl) styrene, p- (4-
Fluorophenyl) styrene, p- (4-chlorophenyl)
Styrene, p- (4-bromophenyl) styrene, p-benzylstyrene, p- (4-fluorobenzyl) styrene, p
-(4-chlorobenzyl) styrene, p-methoxymethylstyrene, p-ethoxymethylstyrene, p-n-propyloxymethylstyrene, p-iso-propyloxymethylstyrene, p-formylstyrene, p-acetylstyrene, p -Benzoylstyrene, p-methoxycarbonylstyrene, p-ethoxycarbonylstyrene, p-phenoxycarbonylstyrene, p-benzyloxycarbonylstyrene, p-methoxystyrene, p-ethoxystyrene, p-n-propoxystyrene, p-iso- Propoxystyrene, p-n-butoxystyrene, p-iso-butoxystyrene, p-sec-butoxystyrene, p-tert-butoxystyrene, p-n-amyloxystyrene, p-iso-amyloxystyrene, p-sec -Amyloxystyrene,
p-tert-amyloxystyrene, p-cyclopropyloxystyrene, p-cyclopropylmethyloxystyrene, p-cyclobutyloxystyrene, p-cyclopentyloxystyrene, p-cyclohexyloxystyrene, p-trifluoromethoxystyrene, p -Pentafluoroethoxystyrene, p-chloromethoxystyrene, p
-(2-chloroethoxy) styrene, p-bromomethoxystyrene, p- (2-bromoethoxy) styrene, p-phenoxystyrene, p- (4-methylphenyloxy) styrene, p- (4-fluorophenyloxy) Styrene, p- (4
-Chlorophenyloxy) styrene, p- (4-bromophenyloxy) styrene, p- (4-methoxyphenyloxy) styrene, p- (4-ethoxyphenyloxy) styrene, p- (4-tert-butoxyphenyloxy) styrene,
p- (4-nitrophenyloxy) styrene, p-benzyloxystyrene, p- (4-methylbenzyloxy) styrene, p-methoxymethoxystyrene, p- (1-ethoxyethoxy) styrene, p- (2-tetrahydro) (Pyranyloxy) styrene, p-acetoxystyrene, p-tert-butylcarbonyloxystyrene, p-benzyloxycarbonyloxystyrene, p-methoxycarbonyloxystyrene, p-tert-butoxycarbonyloxystyrene, p-trimethylsilyloxystyrene, Examples include p-tert-butyldimethylsilyloxystyrene and m-nitrostyrene. The position of the substituent on the benzene nucleus of the above substituted styrene derivative may be any position of ortho, meta and para.

Furthermore, examples of styrene derivatives of formula (II), (IIa) or (IIb) having two or more substituents on the benzene nucleus include 2,3-dichlorostyrene,
2,4-dichlorostyrene, 2,5-dichlorostyrene,
2,6-dichlorostyrene, 3,4-dichlorostyrene,
3,5-dichlorostyrene, 2,3-dibromostyrene,
2,4-dibromostyrene, 2,5-dibromostyrene,
2,3-difluorostyrene, 2,4-difluorostyrene, 2,5-difluorostyrene, 2,6-difluorostyrene, 3,4-difluorostyrene, 3,5-difluorostyrene, 2,3,4,5, 6-pentafluorostyrene, 2,
4,6-trimethylstyrene, 2,3-dimethylstyrene,
2,4-dimethylstyrene, 2,5-dimethylstyrene,
2,6-dimethylstyrene, 2,3-dimethoxystyrene,
2,4-dimethoxystyrene, 2,5-dimethoxystyrene, 2,6-dimethoxystyrene, 3,4-dimethoxystyrene, 3,5-dimethoxystyrene, 2,3-methylenedioxystyrene, 3,4-methylenedi Oxystyrene, 2, 3
-Bis (trifluoromethyl) styrene, 2,4-bis (trifluoromethyl) styrene, 2,5-bis (trifluoromethyl) styrene, 2,6-bis (trifluoromethyl) styrene, 3,4-bis (Trifluoromethyl) styrene and 3,5-bis (trifluoromethyl) styrene are included. Further, the styrene derivative is a styrene derivative having a substituent at the α-position and the β-position of the vinyl group of styrene, such as α-methylstyrene, α-ethylstyrene, α-trimethylsilyloxystyrene, α-methoxystyrene, α-. Chlorostyrene, β-methylstyrene, β-methoxystyrene, β-chlorostyrene, β,
β-dimethylstyrene, β, β-dichlorostyrene,
It may be α, β-dimethylstyrene or β-nitrostyrene.

1,2,4-benzenetriol or its derivative used as a polymerization inhibitor in the method of the present invention and added to a styrene derivative has the following general formula (I): (In the formula, R ¹ , R ² and R ⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group,
A substituted or unsubstituted aryl group, especially a phenyl group, a substituted or unsubstituted aralkyl group, especially a benzyl group, a substituted or unsubstituted alkanoyl group, especially an acetyl group, a substituted or unsubstituted aroyl group, especially a benzoyl group, a cyano group, a carboxyl group, Represents an alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a nitro group, or a substituted or unsubstituted amino group, and R ³ , R ⁵ and R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or non-substituted Substituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, especially phenyl group, substituted or unsubstituted aralkyl group, especially benzyl group, substituted or unsubstituted alkanoyl group, especially acetyl group, substituted or unsubstituted aroyl group , Especially benzoyl groups, substituted or unsubstituted alkylsulfonyl groups, substituted Other unsubstituted arylsulfonyl group,
Particularly, a phenylsulfonyl group, or a substituted or unsubstituted carbamoyl group is shown, and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ ,
R ⁴ and R ⁵ , R ⁵ and R ⁶ or R ⁶ and R ¹ may bond to each other to form a carbocyclic group having a substituted or unsubstituted cyclic structure,
The carbon atoms constituting the carbocyclic group within the ring structure may be replaced by oxygen, sulfur or nitrogen atoms,
Further, a double bond may be present in the carbocyclic group, and R ¹ and R ² may be bonded to each other to form a naphthoquinone or anthraquinone structure as a whole compound of the formula (I)) Is a compound represented by.

Among the 1,2,4-benzenetriol derivatives of the general formula (I), the following general formula (Ia) (In the formula, R ¹ , R ² and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group, a haloalkynyl group, a hydroxyalkyl group, an alkoxyalkyl group. Base,
Haloalkoxyalkyl groups, aryl groups, especially phenyl groups, aralkyl groups, especially benzyl groups, alkanoyl groups,
In particular, acetyl group, aroyl group, especially benzoyl group, aryloxyalkyl group, aralkyloxyalkyl group,
Represents an aroyloxyalkyl group, an alkanoyloxyalkyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carboxyalkyl group, an alkoxycarbonylalkyl group, or a carbamoyl group, and R ³ , R ⁵ , and R ⁶ each independently represent hydrogen. Atoms, alkyl groups, alkenyl groups, alkynyl groups, substituted or unsubstituted aryl groups, especially phenyl groups, substituted or unsubstituted aralkyl groups, especially benzyl groups, alkanoyl groups, especially acetyl groups, substituted or unsubstituted aroyl groups, especially benzoyl groups , An alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, especially a phenylsulfonyl group, or a substituted or unsubstituted carbamoyl group, and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and
R ⁵ , R ⁵ and R ⁶ or R ⁶ and R ¹ may be bonded to form a carbocyclic group having a substituted or unsubstituted cyclic structure, or a carbocyclic group having the cyclic structure. A carbon atom may be replaced by an oxygen, sulfur or nitrogen atom, and a double bond may be present in the carbocyclic group, and
It has been found that a compound represented by the formula (Ia) which may form a naphthoquinone or anthraquinone structure as a whole by the combination of R ¹ and R ² ) is more preferable.

The above-mentioned 1,2,4-benzenetriol or a derivative thereof is a known compound and is known by a known method (for example, Zh. Organ. Khim. Vol. 1, (5) 887-889 (196).
It may be the substance produced in 5)) or may be a commercial product.

Specific examples of 1,2,4-benzenetriol or its derivative used as a polymerization inhibitor in the method of the present invention include the following. That is, 1,2,4-benzenetriol, 5-fluoro-1,2,4-benzenetriol, 5-chloro-1,
2,4-benzenetriol, 5-bromo-1,2,4-benzenetriol, 5-iodo-1,2,4-benzenetriol, 5-methyl-1,2,4-benzenetriol, 5-
Ethyl-1,2,4-benzenetriol, 5-n-propyl-1,2,4-benzenetriol, 5-iso-propyl-1,2,4-benzenetriol, 5-n-butyl-1,
2,4-benzenetriol, 5-iso-butyl-1,2,4
-Benzenetriol, 5-sec-butyl-1,2,4-benzenetriol, 5-tert-butyl-1,2,4-benzenetriol, 5-cyclopentyl-1,2,4-benzenetriol, 5-cyclohexyl -1,2,4-benzenetriol, 5-vinyl-1,2,4-benzenetriol,
5-allyl-1,2,4-benzenetriol, 5- (2-propargyl) -1,2,4-benzenetriol, 5-trifluoromethyl-1,2,4-benzenetriol, 5-chloromethyl- 1,2,4-benzenetriol, 5-bromomethyl-1,2,4-benzenetriol, 5-iodomethyl-1,2,4-benzenetriol, 5- (1-chloroethyl) -1,2,4-benzene Triol, 5- (2-chloroethyl) -1,2,4-benzenetriol, 5- (1-bromoethyl) -1,2,4-benzenetriol, 5- (2-bromoethyl) -1,2,4- Benzenetriol, 5-glycidylmethyl-1,2,4-benzenetriol, 5-hydroxymethyl-1,2,4-benzenetriol, 5- (2-hydroxyethyl) -1,2,4-benzenetriol, 5 −
(1-hydroxyethyl) -1,2,4-benzenetriol, 5-methoxymethyl-1,2,4-benzenetriol, 5- (2-methoxyethyl) -1,2,4-benzenetriol, 5- Ethoxymethyl-1,2,4-benzenetriol, 5-chloromethoxymethyl-1,2,4-benzenetriol, 5-phenyl-1,2,4-benzenetriol, 5- (p-tolyl) -1, 2,4-benzenetriol, 5
-(M-tolyl) -1,2,4-benzenetriol, 5- (o
-Tolyl) -1,2,4-benzenetriol, 5- (p-chlorophenyl) -1,2,4-benzenetriol, 5- (m
-Chlorophenyl) -1,2,4-benzenetriol, 5
-(O-Chlorophenyl) -1,2,4-benzenetriol, 5- (p-nitrophenyl) -1,2,4-benzenetriol, 5- (m-nitrophenyl) -1,2,4-benzene Triol, 5- (o-nitrophenyl) -1,2,4-benzenetriol, 5- (2-pyridyl) -1,2,4-benzenetriol, 5- (3-pyridyl) -1,2,4 -Benzenetriol, 5- (4-pyridyl) -1,2,4-benzenetriol, 5-benzyl-1,2,4-benzenetriol, 5- (p-chlorobenzyl) -1,2,4-benzene Triol, 5- (m-chlorobenzyl) -1,2,4-benzenetriol, 5- (o-chlorobenzyl) -1,2,4-benzenetriol, 5- (p-methylbenzyl) -1,2 , 4-
Benzenetriol, 5- (m-methylbenzyl) -1,2,
4-benzenetriol, 5- (o-methylbenzyl) -1,
2,4-benzenetriol, 5- (p-hydroxybenzyl) -1,2,4-benzenetriol, 5- (m-hydroxybenzyl) -1,2,4-benzenetriol, 5- (o-
Hydroxybenzyl) -1,2,4-benzenetriol,
5- (2,3-dihydroxybenzyl) -1,2,4-benzenetriol, 5- (2,4-dihydroxybenzyl) -1,
2,4-benzenetriol, 5- (2,5-dihydroxybenzyl) -1,2,4-benzenetriol, 5- (2,6-dihydroxybenzyl) -1,2,4-benzenetriol,
5- (3,4-dihydroxybenzyl) -1,2,4-benzenetriol, 5- (3,5-dihydroxybenzyl) -1,
2,4-benzenetriol, 5- (2,3,4-trihydroxybenzyl) -1,2,4-benzenetriol, 5-
(3,4,5-Trihydroxybenzyl) -1,2,4-benzenetriol, 5- (2,3,5-trihydroxybenzyl)
-1,2,4-benzenetriol, 5- (2,3,6-trihydroxybenzyl) -1,2,4-benzenetriol, 5
-(2,4,5-trihydroxybenzyl) -1,2,4-benzenetriol, 5- (2,4,6-trihydroxybenzyl) -1,2,4-benzenetriol, 5- (p- Nitrobenzyl) -1,2,4-benzenetriol, 5- (m-nitrobenzyl) -1,2,4-benzenetriol, 5- (o-
Nitrobenzyl) -1,2,4-benzenetriol, 5-
(2-pyridylmethyl) -1,2,4-benzenetriol,
5- (3-pyridylmethyl) -1,2,4-benzenetriol, 5- (4-pyridylmethyl) -1,2,4-benzenetriol, 5-formyl-1,2,4-benzenetriol,
5-acetyl-1,2,4-benzenetriol, 5-propionyl-1,2,4-benzenetriol, 5-benzoyl-1,2,4-benzenetriol, 5- (p-chlorobenzoyl) -1, 2,4-benzenetriol, 5- (m-chlorobenzoyl) -1,2,4-benzenetriol, 5- (o
-Chlorobenzoyl) -1,2,4-benzenetriol,
5- (p-methylbenzoyl) -1,2,4-benzenetriol, 5- (m-methylbenzoyl) -1,2,4-benzenetriol, 5- (o-methylbenzoyl) -1,2,4 -Benzenetriol, 5- (2,3-dihydroxybenzoyl) -1,2,4-benzenetriol, 5- (2,4-dihydroxybenzoyl) -1,2,4-benzenetriol, 5
-(2,5-dihydroxybenzoyl) -1,2,4-benzenetriol, 5- (2,6-dihydroxybenzoyl)-
1,2,4-benzenetriol, 5- (3,4-dihydroxybenzoyl) -1,2,4-benzenetriol, 5-
(3,5-dihydroxybenzoyl) -1,2,4-benzenetriol, 5- (2,3,4-trihydroxybenzoyl)
-1,2,4-benzenetriol, 5- (3,4,5-trihydroxybenzoyl) -1,2,4-benzenetriol,
5- (2,3,5-trihydroxybenzoyl) -1,2,4-
Benzenetriol, 5- (2,3,6-trihydroxybenzoyl) -1,2,4-benzenetriol, 5- (2,4,
5-trihydroxybenzoyl) -1,2,4-benzenetriol, 5- (2,4,6-trihydroxybenzoyl)-
1,2,4-benzenetriol, 5- (p-nitrobenzoyl) -1,2,4-benzenetriol, 5- (m-nitrobenzoyl) -1,2,4-benzenetriol, 5- (p- Nitrobenzoyl) -1,2,4-benzenetriol, 5-
(m-nitrobenzoyl) -1,2,4-benzenetriol, 5- (o-nitrobenzoyl) -1,2,4-benzenetriol, 5-phenoxymethyl-1,2,4-benzenetriol, 5- Benzyloxymethyl-1,2,4-benzenetriol, 5-benzoyloxymethyl-1,2,4-
Benzenetriol, 5-acetyloxymethyl-1,
2,4-benzenetriol, 5-cyano-1,2,4-benzenetriol, 5-nitro-1,2,4-benzenetriol, 5-carboxy-1,2,4-benzenetriol,
5-methoxycarbonyl-1,2,4-benzenetriol, 5-ethoxycarbonyl-1,2,4-benzenetriol, 5- (iso-amyloxycarbonyl) -1,2,4-
Benzenetriol, 5- (n-butoxycarbonyl)-
1,2,4-benzenetriol, 5- (iso-butyloxycarbonyl) -1,2,4-benzenetriol, 5- (n-
Hexadecyloxycarbonyl) -1,2,4-benzenetriol, 5- (n-dodecyloxycarbonyl) -1,2,
4-benzenetriol, 5- (n-octyloxycarbonyl) -1,2,4-benzenetriol, 5- (n-propyloxycarbonyl) -1,2,4-benzenetriol,
5-stearyloxycarbonyl-1,2,4-benzenetriol, 5-carboxymethyl-1,2,4-benzenetriol, 5-methoxycarbonylmethyl-1,2,4-benzenetriol, 5-carbamoyl-1, 2,4-benzenetriol, 5-dimethylaminocarbonyl-1,2,4
-Examples include benzenetriol. One, two,
Substituents on the benzene nucleus of 4-benzenetriol are not limited to the above 5-position substitution products, but also 3-position substitution products, 6-position substitution products, 3,5
-Di-substituted product, 3,6-di-substituted product, 5,6-di-substituted product, 3,5,
It may be in a position to form a 6-tri-substituted product. Also,
When they are di-substituted or tri-substituted, the substituting functional groups may be the same or different.

Further, 1, 2, 4 represented by the general formula (I)
Examples of the benzenetriol derivative include 4- (substituted hydroxy) catechol, 4- (substituted hydroxy) resorcinol, 2,4-di (substituted hydroxy) phenol, 2,5-di (substituted hydroxy) phenol, which are exemplified below.
Also included are 3,4-di (substituted hydroxy) phenols.
That is, 4-methoxycatechol, 4-allyloxycatechol, 4- (2-propynyloxy) catechol, 4-
Cyclohexyloxycatechol, 4-acetoxycatechol, 4-phenoxycatechol, 4- (4-chlorophenoxy) catechol, 4- (3-chlorophenoxy) catechol, 4- (2-chlorophenoxy) catechol, 4- (4-
Trilyloxy) catechol, 4- (3-tolyloxy) catechol, 4- (2-tolyloxy) catechol, 4- (4-hydroxyphenoxy) catechol, 4- (3-hydroxyphenoxy) catechol, 4- (2-hydroxyphenoxy)
Catechol, 4- (4-methoxyphenoxy) catechol,
4- (3-methoxyphenoxy) catechol, 4- (2-methoxyphenoxy) catechol, 4-benzyloxycatechol, 4- (4-methylbenzyloxy) catechol, 4-
(3-Methylbenzyloxy) catechol, 4- (2-methylbenzyloxy) catechol, 4- (4-chlorobenzyloxy) catechol, 4- (3-chlorobenzyloxy) catechol, 4- (2-chlorobenzyloxy) ) Catechol, 4
-(4-hydroxybenzyloxy) catechol, 4- (3-
(Hydroxybenzyloxy) catechol, 4- (2-hydroxybenzyloxy) catechol, 4- (4-nitrobenzyloxy) catechol, 4- (3-nitrobenzyloxy)
Catechol, 4- (2-nitrobenzyloxy) catechol, 4-benzoyloxycatechol, 4- (4-methylbenzoyloxy) catechol, 4- (3-methylbenzoyloxy) catechol, 4- (2-methylbenzoyloxy)
Catechol, 4- (4-chlorobenzoyloxy) catechol, 4- (3-chlorobenzoyloxy) catechol, 4-
(2-chlorobenzoyloxy) catechol, 4- (4-methoxybenzoyloxy) catechol, 4- (3-methoxybenzoyloxy) catechol, 4- (2-methoxybenzoyloxy) catechol, 4- (4-nitrobenzoyloxy) ) Catechol, 4- (3-nitrobenzoyloxy) catechol, 4- (2-nitrobenzoyloxy) catechol,
4- (2-pyridyloxy) catechol, 4- (3-pyridyloxy) catechol, 4- (4-pyridyloxy) catechol; or 4-methoxyresorcinol, 4-allyloxyresorcinol, 4- (2-propynyloxy) Resorcinol, 4-cyclohexyloxyresorcinol, 4
-Acetoxyresorcinol, 4-phenoxyresorcinol, 4- (4-chlorophenoxy) resorcinol, 4
-(3-Chlorophenoxy) resorcinol, 4- (2-chlorophenoxy) resorcinol, 4- (4-tolyloxy)
Resorcinol, 4- (3-tolyloxy) resorcinol, 4- (2-tolyloxy) resorcinol, 4- (4-hydroxyphenoxy) resorcinol, 4- (3-hydroxyphenoxy) resorcinol, 4- (2-hydroxyphenoxy) resorcinol, 4- (4-methoxyphenoxy)
Resorcinol, 4- (3-methoxyphenoxy) resorcinol, 4- (2-methoxyphenoxy) resorcinol,
4-benzyloxyresorcinol, 4- (4-methylbenzyloxy) resorcinol, 4- (3-methylbenzyloxy) resorcinol, 4- (2-methylbenzyloxy)
Resorcinol, 4- (4-chlorobenzyloxy) resorcinol, 4- (3-chlorobenzyloxy) resorcinol, 4- (2-chlorobenzyloxy) resorcinol, 4
-(4-hydroxybenzyloxy) resorcinol, 4-
(3-hydroxybenzyloxy) resorcinol, 4- (2
-Hydroxybenzyloxy) resorcinol, 4- (4-
(Nitrobenzyloxy) resorcinol, 4- (3-nitrobenzyloxy) resorcinol, 4- (2-nitrobenzyloxy) resorcinol, 4-benzoyloxyresorcinol, 4- (4-methylbenzoyloxy) resorcinol, 4- (3- Methylbenzoyloxy) resorcinol, 4- (2-methylbenzoyloxy) resorcinol,
4- (4-chlorobenzoyloxy) resorcinol, 4-
(3-chlorobenzoyloxy) resorcinol, 4- (2-
(Chlorobenzoyloxy) resorcinol, 4- (4-methoxybenzoyloxy) resorcinol, 4- (3-methoxybenzoyloxy) resorcinol, 4- (2-methoxybenzoyloxy) resorcinol, 4- (4-nitrobenzoyloxy) resorcinol, 4- (3-nitrobenzoyloxy) resorcinol, 4- (2-nitrobenzoyloxy) resorcinol, 4- (2-pyridyloxy) resorcinol, 4- (3-pyridyloxy) resorcinol, 4
-(4-Pyridyloxy) resorcinol; or 2,4
-Dimethoxyphenol, 2,4-diallyloxyphenol, 2,4-bis (2-propynyloxy) phenol,
2,4-dicyclohexyloxyphenol, 2,4-diacetoxyphenol, 2,4-diphenoxyphenol,
2,4-bis (4-chlorophenoxy) phenol, 2,4-
Bis (3-chlorophenoxy) phenol, 2,4-bis (2
-Chlorophenoxy) phenol, 2,4-bis (4-tolyloxy) phenol, 2,4-bis (3-tolyloxy) phenol, 2,4-bis (2-tolyloxy) phenol,
2,4-bis (4-hydroxyphenoxy) phenol, 2,
4-bis (3-hydroxyphenoxy) phenol, 2,4-
Bis (2-hydroxyphenoxy) phenol, 2,4-bis (4-methoxyphenoxy) phenol, 2,4-bis (3
-Methoxyphenoxy) phenol, 2,4-bis (2-methoxyphenoxy) phenol, 2,4-dibenzyloxyphenol, 2,4-bis (4-methylbenzyloxy)
Phenol, 2,4-bis (3-methylbenzyloxy) phenol, 2,4-bis (2-methylbenzyloxy) phenol, 2,4-bis (4-chlorobenzyloxy) phenol, 2,4-bis ( 3-chlorobenzyloxy) phenol, 2,4-bis (2-chlorobenzyloxy) phenol, 2,4-bis (4-hydroxybenzyloxy) phenol, 2,4-bis (3-hydroxybenzyloxy) phenol, 2,4-bis (2-hydroxybenzyloxy) phenol, 2,4-bis (4-nitrobenzyloxy) phenol, 2,4-bis (3-nitrobenzyloxy) phenol, 2,4-bis (2- Nitrobenzyloxy) phenol, 2,4-dibenzoyloxyphenol, 2,4-bis
(4-methylbenzoyloxy) phenol, 2,4-bis
(3-methylbenzoyloxy) phenol, 2,4-bis
(2-Methylbenzoyloxy) phenol, 2,4-bis
(4-chlorobenzoyloxy) phenol, 2,4-bis
(3-chlorobenzoyloxy) phenol, 2,4-bis
(2-chlorobenzoyloxy) phenol, 2,4-bis
(4-Methoxybenzoyloxy) phenol, 2,4-bis (3-methoxybenzoyloxy) phenol, 2,4-
Bis (2-methoxybenzoyloxy) phenol, 2,4
-Bis (4-nitrobenzoyloxy) phenol, 2,4
-Bis (3-nitrobenzoyloxy) phenol, 2,4
-Bis (2-nitrobenzoyloxy) phenol, 2,4
-Bis (2-pyridyloxy) phenol, 2,4-bis (3
-Pyridyloxy) phenol, 2,4-bis (4-pyridyloxy) phenol, 2-acetoxy-4-methoxyphenol, 4-acetoxy-2-methoxyphenol, 2
-Benzyloxy-4-methoxyphenol, 4-benzyloxy-2-methoxyphenol, 2-benzoyloxy-4-methoxyphenol, 4-benzoyloxy-2
-Methoxyphenol; or 2,5-dimethoxyphenol, 2,5-diallyloxyphenol, 2,5-bis
(2-propynyloxy) phenol, 2,5-dicyclohexyloxyphenol, 2,5-diacetoxyphenol, 2,5-diphenoxyphenol, 2,5-bis (4-chlorophenoxy) phenol, 2,5-bis (3-chlorophenoxy) phenol, 2,5-bis (2-chlorophenoxy) phenol, 2,5-bis (4-tolyloxy) phenol, 2,5-bis (3-tolyloxy) phenol, 2,5-
Bis (2-tolyloxy) phenol, 2,5-bis (4-hydroxyphenoxy) phenol, 2,5-bis (3-hydroxyphenoxy) phenol, 2,5-bis (2-hydroxyphenoxy) phenol, 2,5 -Bis (4-methoxyphenoxy) phenol, 2,5-bis (3-methoxyphenoxy) phenol, 2,5-bis (2-methoxyphenoxy) phenol, 2,5-dibenzyloxyphenol,
2,5-bis (4-methylbenzyloxy) phenol, 2,
5-bis (3-methylbenzyloxy) phenol, 2,5-
Bis (2-methylbenzyloxy) phenol, 2,5-bis (4-chlorobenzyloxy) phenol, 2,5-bis
(3-chlorobenzyloxy) phenol, 2,5-bis (2
-Chlorobenzyloxy) phenol, 2,5-bis (4-
Hydroxybenzyloxy) phenol, 2,5-bis (3
-Hydroxybenzyloxy) phenol, 2,5-bis
(2-Hydroxybenzyloxy) phenol, 2,5-bis (4-nitrobenzyloxy) phenol, 2,5-bis
(3-Nitrobenzyloxy) phenol, 2,5-bis (2
-Nitrobenzyloxy) phenol, 2,5-dibenzoyloxyphenol, 2,5-bis (4-methylbenzoyloxy) phenol, 2,5-bis (3-methylbenzoyloxy) phenol, 2,5-bis ( 2-methylbenzoyloxy) phenol, 2,5-bis (4-chlorobenzoyloxy) phenol, 2,5-bis (3-chlorobenzoyloxy) phenol, 2,5-bis (2-chlorobenzoyloxy) phenol, 2,5-bis (4-methoxybenzoyloxy) phenol, 2,5-bis (3-methoxybenzoyloxy) phenol, 2,5-bis (2-methoxybenzoyloxy) phenol, 2,5-bis (4- Nitrobenzoyloxy) phenol, 2,5-bis (3-nitrobenzoyloxy) phenol, 2,5-bis (2-nitrobenzoyloxy) phenol, 2,5-bis (2-pyridylo) Xy) phenol, 2,5-bis (3-pyridyloxy) phenol, 2,5-bis (4-pyridyloxy) phenol, 2-acetoxy-5-methoxyphenol, 5-acetoxy-2-methoxyphenol, 2- Benzyloxy-
5-methoxyphenol, 5-benzyloxy-2-methoxyphenol, 2-benzoyloxy-5-methoxyphenol, 5-benzoyloxy-2-methoxyphenol; or 3,4-dimethoxyphenol, 3,4-diallyloxyphenol , 3,4-bis (2-propynyloxy) phenol, 3,4-dicyclohexyloxyphenol, 3,4-diacetoxyphenol, 3,4-diphenoxyphenol, 3,4-bis (4-chlorophenoxy) phenol , 3,4-bis (3-chlorophenoxy) phenol, 3,4-bis (2-chlorophenoxy) phenol, 3,
4-bis (4-tolyloxy) phenol, 3,4-bis (3-
Trilyloxy) phenol, 3,4-bis (2-tolyloxy) phenol, 3,4-bis (4-hydroxyphenoxy)
Phenol, 3,4-bis (3-hydroxyphenoxy) phenol, 3,4-bis (2-hydroxyphenoxy) phenol, 3,4-bis (4-methoxyphenoxy) phenol, 3,4-bis (3-methoxy) Phenoxy) phenol,
3,4-bis (2-methoxyphenoxy) phenol, 3,4
-Dibenzyloxyphenol, 3,4-bis (4-methylbenzyloxy) phenol, 3,4-bis (3-methylbenzyloxy) phenol, 3,4-bis (2-methylbenzyloxy) phenol, 3, 4-bis (4-chlorobenzyloxy) phenol, 3,4-bis (3-chlorobenzyloxy) phenol, 3,4-bis (2-chlorobenzyloxy) phenol, 3,4-bis (4-hydroxybenzyl) (Oxy) phenol, 3,4-bis (3-hydroxybenzyloxy) phenol, 3,4-bis (2-hydroxybenzyloxy) phenol, 3,4-bis (4-nitrobenzyloxy) phenol, 3,4- Bis (3-nitrobenzyloxy) phenol, 3,4-bis (2-nitrobenzyloxy) phenol, 3,4-dibenzoyloxyphenol, 3,4-bis (4-methylbenzoyloxy) phenol , 3,4-bis (3-methylbenzoyloxy) phenol, 3,4-bis (2-methylbenzoyloxy) phenol, 3,4-bis (4-chlorobenzoyloxy) phenol, 3,4-bis (3 -Chlorobenzoyloxy) phenol, 3,4-bis (2-chlorobenzoyloxy) phenol, 3,4-bis (4-methoxybenzoyloxy) phenol, 3,4-bis (3-methoxybenzoyloxy) phenol, 3 , 4-bis (2-methoxybenzoyloxy) phenol, 3,4-bis (4-nitrobenzoyloxy) phenol, 3,4-bis (3-nitrobenzoyloxy) phenol, 3,4-bis (2-nitro) Benzoyloxy) phenol, 3,4-bis (2-pyridyloxy) phenol, 3,4-bis (3-pyridyloxy) phenol, 3,4
-Bis (4-pyridyloxy) phenol, 3,4-methylenedioxyphenol, 3-acetoxy-4-methoxyphenol, 4-acetoxy-3-methoxyphenol, 3
-Benzyloxy-4-methoxyphenol, 4-benzyloxy-3-methoxyphenol, 3-benzoyloxy-4-methoxyphenol, 4-benzoyloxy-3
-Methoxyphenol; or 1,2,4-trimethoxybenzene, 1,2,4-triallyloxybenzene, 1,
2,4-Tris (2-propynyloxy) benzene, 1,2,4
-Tricyclohexyloxybenzene, 1,2,4-triacetoxybenzene, 1,2,4-triphenoxybenzene, 1,2,4-tris (4-chlorophenoxy) benzene,
1,2,4-tris (3-chlorophenoxy) benzene, 1,
2,4-Tris (2-chlorophenoxy) benzene, 1,2,4
-Tris (4-tolyloxy) benzene, 1,2,4-tris
(3-Tolyloxy) benzene, 1,2,4-tris (2-tolyloxy) benzene, 1,2,4-tris (4-hydroxyphenoxy) benzene, 1,2,4-tris (3-hydroxyphenoxy) benzene , 1,2,4-Tris (2-hydroxyphenoxy) benzene, 1,2,4-tris (4-methoxyphenoxy) benzene, 1,2,4-tris (3-methoxyphenoxy) benzene, 1,2, 4-tris (2-methoxyphenoxy) benzene, 1,2,4-tribenzyloxybenzene,
1,2,4-tris (4-methylbenzyloxy) benzene,
1,2,4-tris (3-methylbenzyloxy) benzene,
1,2,4-tris (2-methylbenzyloxy) benzene,
1,2,4-tris (4-chlorobenzyloxy) benzene,
1,2,4-tris (3-chlorobenzyloxy) benzene,
1,2,4-tris (2-chlorobenzyloxy) benzene,
1,2,4-triz (4-hydroxybenzyloxy) benzene, 1,2,4-tris (3-hydroxybenzyloxy) benzene, 1,2,4-tris (2-hydroxybenzyloxy) benzene, 1, 2,4-Tris (4-nitrobenzyloxy) benzene, 1,2,4-Tris (3-nitrobenzyloxy) benzene, 1,2,4-Tris (2-nitrobenzyloxy) benzene, 1,2, 4-tribenzoyloxybenzene, 1,2,4-tris (4-methylbenzoyloxy) benzene, 1,2,4-tris (3-methylbenzoyloxy) benzene, 1,2,4-tris (2-methyl) Benzoyloxy)
Benzene, 1,2,4-tris (4-chlorobenzoyloxy) benzene, 1,2,4-tris (3-chlorobenzoyloxy) benzene, 1,2,4-tris (2-chlorobenzoyloxy) benzene, 1,2,4-tris (4-methoxybenzoyloxy) benzene, 1,2,4-tris (3-methoxybenzoyloxy) benzene, 1,2,4-tris (2-methoxybenzoyloxy) benzene, 1, 2,4-Tris (4-nitrobenzoyloxy) benzene, 1,2,4-Tris (3-
Nitrobenzoyloxy) benzene, 1,2,4-tris (2
-Nitrobenzoyloxy) benzene, 1,2,4-tris
(2-Pyridyloxy) benzene, 1,2,4-tris (3-pyridyloxy) benzene, 1,2,4-tris (4-pyridyloxy) benzene, 4-methoxy-1,2-methylenedioxybenzene , 4-benzyloxy-1,2-methylenedioxybenzene, 4-benzoyloxy-1,2-methylenedioxybenzene, 1-acetoxy-2,4-dimethoxybenzene, 2-acetoxy-1,4-dimethoxybenzene , 4-acetoxy-1,2-dimethoxybenzene, 1-benzyloxy-2,4-dimethoxybenzene, 2-benzyloxy-1,4-dimethoxybenzene, 4-benzyloxy-1,2-dimethoxybenzene, 1- Benzoyloxy-2,4-dimethoxybenzene, 2-benzoyloxy-1,4-dimethoxybenzene, 4-benzoyloxy-
1,2-dimethoxybenzene, 5,6,8-trihydroxynaphthoquinone and purpurine are also represented by general formula (I).
Included in 1,2,4-benzenetriol derivatives.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is carried out as follows. That is, immediately after the styrene or styrene derivative of the general formula (II) to be distilled is produced, 1,2,4-benzenetriol of the general formula (I) or its derivative which is a polymerization inhibitor is added. After this, a distillation operation may be performed.

Of the general formula (I) used in the process of the invention:
The amount of 1,2,4-benzenetriol or its derivative added is such that the amount of 1,2,4-benzenetriol or its derivative is
Substituents X ¹ , X ² , X ³ of styrene or styrene derivative of
It is defined experimentally by the types of Y, Z and Z ¹ , the distillation temperature and the distillation pressure, etc., but is generally found to be 10 to 100,000 ppm with respect to the styrene or styrene derivative of the general formula (II) to be distilled. , Preferably in the range of 100 to 10,000 ppm. Distillation temperature is usually 20 ~ 200 ℃, preferably 40
The temperature is ~ 150 ° C. The distillation of styrene or oxystyrene derivative is usually carried out under reduced pressure, usually 0.0001 to 500 mmHg, preferably 0.0001 to 10 mmHg.
Done under pressure.

[0021]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Example 1 A polymerization inhibitor was added to 100 g of PTBST (that is, p-tert-butoxystyrene) immediately after being synthesized by the method of Japanese Patent Publication No. 4-71896 in a four-necked flask equipped with a distillation condenser, a thermometer and a stirrer. As a result, 0.05 g of 1,2,4-benzenetriol (concentration of 500 ppm) was added to the mixture. This mixture (in liquid form) 13
The mixture was distilled at 0 ° C. under a reduced pressure of 5 mmHg for 48 hours with stirring. By this distillation step, 95.1 g of PTBST could be distilled from the flask. At the bottom of the flask, about 4.9 g of highly viscous liquid substance remained without being distilled. The recovery rate (%) of PTBST which was distilled and recovered from the flask was calculated by the following formula. Recovery rate (%) = [(PTBST distilled from the flask by distillation
Weight) / (weight of PTBST charged into the flask before distillation)] × 100 The measured recovery rate (%) is shown in Table 1 below.

[0022]

Example 2 The same distillation step as in Example 1 was operated except that purpurine was used in place of the polymerization inhibitor 1,2,4-benzenetriol used in Example 1.

Example 3 The same distillation step as in Example 1 was operated except that esculetin was used in place of the polymerization inhibitor 1,2,4-benzenetriol used in Example 1.

Example 4 The same distillation step as in Example 1 was operated except that sesamol was used in place of the polymerization inhibitor 1,2,4-benzenetriol used in Example 1.

Example 5 The same distillation process as in Example 1 was performed except that 1,2,4-trimethoxybenzene was used instead of the polymerization inhibitor 1,2,4-benzenetriol used in Example 1. Operated.

[0023]

Example 6 The same distillation process as in Example 1 was repeated except that 1,2,4-triacetoxybenzene was used in place of the polymerization inhibitor 1,2,4-benzenetriol used in Example 1. Operated.

[Example 7] The same distillation as in Example 1 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the PTBST to be distilled used in Example 1. The process was operated.

[Example 8] Purpurin similar to Example 2 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the distilled PTBST used in Example 2. The distillation process was operated in the presence of

Example 9 Esculetin was prepared in the same manner as in Example 3 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the distilled PTBST used in Example 3. The distillation process was operated in the presence of

[Example 10] Purpurin similar to Example 2 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the distilled PTBST used in Example 4. The distillation process was operated in the presence of

[Example 11] Esculetin was prepared in the same manner as in Example 3 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the distilled PTBST used in Example 5. The distillation process was operated in the presence of

Example 12 Esculetin was prepared in the same manner as in Example 3 except that MTBST (synthesized by the method described in JP-A-2-160739) was used in place of the distilled PTBST used in Example 6. The distillation process was operated in the presence of

[0024]

Comparative Example 1 1, 2 used as a polymerization inhibitor in Example 1,
The distillation step of PTBST was operated in the same manner as in Example 1 except that a known polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt was used in place of 4-benzenetriol.

Comparative Example 2 1, 2, which was used as a polymerization inhibitor in Example 7,
The MTBST distillation step was operated in the same manner as in Example 7 except that p-tert-butylcatechol, which is a known polymerization inhibitor, was used instead of 4-benzenetriol.

[Comparative Example 3] 1, 2, which was used as a polymerization inhibitor in Example 1,
The distillation step of PTBST was operated in the same manner as in Example 1 except that resorcinol (that is, 1,3-benzenediol) which is a known polymerization inhibitor was used in place of 4-benzenetriol.

[Comparative Example 4] 1, 2, which was used as a polymerization inhibitor in Example 1,
Similar to Example 1 except that hydroquinone, which is a known polymerization inhibitor, was used in place of 4-benzenetriol.
The distillation process of PTBST was operated.

Comparative Example 5 1, 2 used as the polymerization inhibitor in Example 1,
PTBST was prepared in the same manner as in Example 1 except that catechol, which is a known polymerization inhibitor, was used instead of 4-benzenetriol.
The distillation process was operated.

The measured values of the recovery rates of the styrene derivatives obtained in Examples 1 to 12 and Comparative Examples 1 to 5 are shown in Table 1 below.
Are summarized in.

The following effects are brought about by implementing the present invention. That is, formation of a highly viscous polymeric substance is prevented during the distillation process, and the recovery rate of the distilled styrene or styrene derivative is high. Therefore, the styrene or styrene derivative distillation method of the present invention solves the problems of the conventional distillation methods and is highly useful as an industrial method.

Claims (7)

[Claims] 1. A method comprising adding 1,2,4-benzenetriol or a derivative thereof as a polymerization inhibitor to styrene or a styrene derivative, and distilling the styrene or the styrene derivative in the presence of the polymerization inhibitor. Method of distilling styrene or styrene derivatives. 2. A 1,2,4-added as a polymerization inhibitor
Benzenetriol or its derivative is represented by the following general formula (I) (In the formula, R ¹ , R ² and R ⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group,
A substituted or unsubstituted aryl group, especially a phenyl group, a substituted or unsubstituted aralkyl group, especially a benzyl group, a substituted or unsubstituted alkanoyl group, especially an acetyl group, a substituted or unsubstituted aroyl group, especially a benzoyl group, a cyano group, a carboxyl group, Represents an alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a nitro group, or a substituted or unsubstituted amino group, and R ³ , R ⁵ and R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or non-substituted Substituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, especially phenyl group, substituted or unsubstituted aralkyl group, especially benzyl group, substituted or unsubstituted alkanoyl group, especially acetyl group, substituted or unsubstituted aroyl group , Especially benzoyl groups, substituted or unsubstituted alkylsulfonyl groups, substituted Other unsubstituted arylsulfonyl group,
Particularly, a phenylsulfonyl group, or a substituted or unsubstituted carbamoyl group is shown, and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ ,
R ⁴ and R ⁵ , R ⁵ and R ⁶ or R ⁶ and R ¹ may bond to each other to form a carbocyclic group having a substituted or unsubstituted cyclic structure,
The carbon atom constituting the carbocyclic group of the cyclic structure is oxygen,
It may be replaced by a sulfur or nitrogen atom, a double bond may be present in the carbocyclic group, and R ¹ and R ² may be bonded to each other to form a compound of the formula (I). The method according to claim 1, wherein the compound is represented by a naphthoquinone or anthraquinone structure as a whole). 3. A 1,2,4-added as a polymerization inhibitor
Benzenetriol or its derivative has the following general formula (Ia) (In the formula, R ¹ , R ² and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group, a haloalkynyl group, a hydroxyalkyl group, an alkoxyalkyl group. Base,
Haloalkoxyalkyl groups, aryl groups, especially phenyl groups, aralkyl groups, especially benzyl groups, alkanoyl groups,
In particular, acetyl group, aroyl group, especially benzoyl group, aryloxyalkyl group, aralkyloxyalkyl group,
Represents an aroyloxyalkyl group, an alkanoyloxyalkyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carboxyalkyl group, an alkoxycarbonylalkyl group, or a carbamoyl group, and R ³ , R ⁵ , and R ⁶ each independently represent hydrogen. Atoms, alkyl groups, alkenyl groups, alkynyl groups, substituted or unsubstituted aryl groups, especially phenyl groups, substituted or unsubstituted aralkyl groups, especially benzyl groups, alkanoyl groups, especially acetyl groups, substituted or unsubstituted aroyl groups, especially benzoyl groups , An alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, especially a phenylsulfonyl group, or a substituted or unsubstituted carbamoyl group, and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and
R ⁵ , R ⁵ and R ⁶ or R ⁶ and R ¹ may be bonded to form a carbocyclic group having a substituted or unsubstituted cyclic structure, or a carbocyclic group having the cyclic structure. A carbon atom may be replaced by an oxygen, sulfur or nitrogen atom, and a double bond may be present in the carbocyclic group, and
The method according to claim ¹ , wherein R ¹ and R ² are bonded to each other to form a naphthoquinone or anthraquinone structure as a whole of the compound of formula (Ia). 4. The styrene or styrene derivative to be distilled is represented by the following general formula (II): (In the formula, Y is a hydrogen atom, an amino group, an alkyl group, an alkenyl group, an alkynyl group, a halogen atom, a haloalkyl group, an aryl group, particularly a phenyl group, an aralkyl group, particularly a benzyl group, an alkoxyalkyl group, a nitro group, an alkanoyl group. , Especially acetyl group, aroyl group, especially benzoyl group, alkoxycarbonyl group, arylalkoxycarbonyl group, alkoxy group, haloalkoxy group, aryloxy group, aralkyloxy group, alkoxyalkyloxy group, alkanoyloxy group, alkoxycarbonyloxy group, Represents an aralkyloxycarbonyloxy group, or an alkylsilyloxy group, n is 0 or an integer from 1 to 4, and when n is 2 or more, Y represents the same or different n groups. may indicate further X ^1, X ^2, X ^3, it Independently, a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a compound represented by an alkyl silyl group or a nitro group) The method of claim 1, 2 or 3. 5. The styrene derivative to be distilled is represented by the following general formula (IIa): (In the formula, Z is an alkyl group, a haloalkyl group, an aryl group, particularly a phenyl group, an aralkyl group, especially a benzyl group,
An alkoxyalkyl group, an alkanoyl group, particularly an acetyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group, and further X ¹ ,
X ² and X ³ are each independently a hydrogen atom, an alkyl group,
The method according to claim 1, 2 or 3, which is an oxystyrene derivative represented by an alkoxy group, a halogen atom, an alkylsilyloxy group or a nitro group, and n is an integer of 1 to 4. 6. The styrene derivative to be distilled is represented by the following general formula (IIb): (In the formula, Z'is an alkyl group, a haloalkyl group, an aryl group, particularly a phenyl group, an aralkyl group, especially a benzyl group,
The method according to claim 1, 2 or 3, which is an oxystyrene derivative represented by an alkoxyalkyl group, an alkanoyl group, particularly an acetyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group. 7. The method according to claim 1, wherein the styrene derivative to be distilled is tert-butoxystyrene.