JP2003081899A - 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, wherein formation of highly viscous polymer like materials is prevented and recovery percentage of the distilled styrene derivative is high. SOLUTION: This method comprises using anthrone as the polymerization inhibitor and distilling a styrene derivative represented by general formula (I), such as p-tert-butoxystyrene, p-acetoxystyrene, 3,4-dimethoxystyrene or α-methyl-m-chlorostyrene using anthrone as the polymerization inhibitor.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides an improved technique of a method for distilling styrene or a styrene derivative useful as a raw material for medical and agricultural chemicals, functional polymers, polymer synthesis, etc. for the purpose of purification after the synthesis. It is about.

[0002]

2. Description of the Related Art Among styrene derivatives, for example, p-te
rt-Butoxystyrene (hereinafter abbreviated as “PTBST”. “PTBST” is a registered trademark of the applicant) is an ultra-L
It is known to be extremely useful as a resist raw material used for SI applications and the like (JP-A-59-199).
705, 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.
-160739).

The following methods are known as methods for synthesizing styrene derivatives. p-chlorostyrene, 3,4-dichlorostyrene, α
Styrene derivatives such as -methyl-m-chlorostyrene, p-trifluoromethylstyrene, p-methylstyrene, p-methoxystyrene are the corresponding N-acyl-β-
A method (Japanese Patent Laid-Open No. 61-212526) obtained by treating phenethylamines with a base is known. Styrene derivatives such as p-acetoxystyrene and p-trimethylsilyloxystyrene are known to be obtained by reacting the corresponding substituted benzaldehyde with dibromomethane (Japanese Patent Laid-Open No. 8-157410). Tert-butoxystyrene such as PTBST and MTBST is synthesized by preparing a Grignard reagent from halogen-substituted styrene such as chlorostyrene, bromostyrene and iodostyrene and metallic magnesium, and then reacting this with perbenzoic acid tert-butyl ester. A method (Japanese Patent Application Laid-Open No. 59-199705) is known. tert-butoxyphenyl chloride, tert-
A method in which a Grignard reagent is prepared from tert-butoxyphenyl halide such as butoxyphenyl bromide or tert-butoxyphenyl iodide and magnesium, and then coupled with vinyl halide such as vinyl chloride or vinyl bromide ( Japanese Patent Publication No. 4-71896 and Japanese Patent Laid-Open No. 16073/1990.
No. 9) is known.

In the above-mentioned method for synthesizing a styrene derivative, the synthesized target compound 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. Further, the generated polymeric substance causes troubles such as an abnormality in the degree of pressure reduction due to blockage of the distillation column or the pipe in the distillation column, the distillation can, the piping, etc., and difficulty in cleaning due to adhesion of the polymeric substance. Sometimes. 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. For example, tert- such as PTBST and MTBST
In the distillation of butoxystyrene, a method of performing distillation in the presence of 4-tert-butylcatechol (Patent Publication 4-
No. 71896, JP-A-2-160739).
Alternatively, a method of performing distillation in the presence of N-nitrosophenylhydroxylamine aluminum salt, N-nitrosophenylhydroxylamine ammonium salt, 2,4-dinitrophenol, or the like (Japanese Patent Laid-Open No. 2000-327617) is known.

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 styrene or a styrene derivative, and A highly viscous polymeric substance is formed, which causes troubles such as blockage of the distillation column or piping in the distillation column or distillation can, abnormal pressure reduction, and difficulty in cleaning due to adhesion of the polymeric substance. There are many. Even if such 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 or styrene derivatives have not been satisfactory.

[0006]

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. That is, there is almost no formation of a polymeric substance that occurs in the conventional method, and styrene or p-chlorostyrene, 3,4
-Dichlorostyrene, α-methyl-m-chlorostyrene, p-trifluoromethylstyrene, p-methylstyrene, p-methoxystyrene, p-acetoxystyrene, p-trimethylsilyloxystyrene, PTBST
Another object of the present invention is to provide a novel economical distillation method capable of purifying a styrene derivative such as MTBST by distillation.

[0007]

[Means for Solving the Problems] The present inventors have conducted extensive studies and studied in order to solve the conventional problems. As a result, in the distillation step after the production of styrene or a styrene derivative, by adding anthrone as a polymerization inhibitor and distilling in the presence of it, a high recovery of styrene or a styrene derivative can be achieved without generating a polymeric substance. It was found that the rate can be distilled. The present invention has been completed based on this finding.

Therefore, the present invention provides a method for distilling styrene or a styrene derivative, which comprises distilling styrene or a styrene derivative using anthrone as a polymerization inhibitor.

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 to be distilled in the method of the present invention is represented by the following general formula (I)

[Chemical 4] (In the formula, R represents 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. Group, aroyl group, especially benzoyl group, alkoxycarbonyl group, arylalkoxycarbonyl group, alkoxy group, haloalkoxy group, aryloxy group, aralkyloxy group, alkoxyalkyloxy group, alkanoyloxy group, alkoxycarbonyloxy group, aralkyloxycarbonyl Represents an oxy group or an alkylsilyloxy group, n is 0 or an integer from 1 to 5, and when n is 2 or more, R may be the same or different, and further, X ₁ , X ₂ , X ₃ is the same or different, water Atom, an alkyl group, an alkoxy group, there are halogen atoms, a compound represented by an alkyl silyl group or a nitro group), in particular the following general formula (I
a)

[Chemical 5] (In the formula, R ′ represents an alkyl group, a haloalkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, an alkanoyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group, and n is 1 to 5 Is an integer, and when n is 2 or more, R ′ may be the same or different, and further, X ₁ , X ₂ , X
₃ are the same or different and each is 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 more preferably the following general formula (Ib)

[Chemical 6] (In the formula, R '' represents an alkyl group, a haloalkyl group, an aryl group, particularly a phenyl group, an aralkyl group, particularly a benzyl group, an alkoxyalkyl group, an alkanoyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group. ).

Specific examples of the styrene or styrene derivative of the general formula (I), (Ia) or (Ib) include:
For example: That is, styrene, p
-Aminostyrene, p-methylstyrene, p-ethylstyrene, pn-propylstyrene, p-isopropylstyrene, pn-butylstyrene, p-isobutylstyrene, p-sec-butylstyrene, p-tert-
Butyl styrene, pn-amyl styrene, p-isoamyl styrene, p-sec-amyl styrene, p-te
rt-amyl styrene, p-cyclopropyl styrene,
p-cyclopropylmethylstyrene, p-cyclopentylstyrene, p-cyclohexylstyrene, p-vinylstyrene, p-allylstyrene, p-ethynylstyrene, p-propargylstyrene, p-fluorostyrene, p-chlorostyrene, p-bromo. Styrene, p-iodostyrene, p-chloromethylstyrene, p-bromomethylstyrene, p-iodomethylstyrene, p-trifluoromethylstyrene, 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-isopropyloxymethylstyrene, p-formylstyrene, p-acetylstyrene, p-benzoylstyrene, p-methoxycarbonylstyrene, p-ethoxycarbonylstyrene, p-phenoxycarbonylstyrene, p-benzyl Oxycarbonyl styrene, p-methoxy styrene, p
-Ethoxystyrene, pn-propoxystyrene, p
-Isopropoxystyrene, pn-butoxystyrene, p-isobutoxystyrene, p-sec-butoxystyrene, p-tert-butoxystyrene, pn-
Amyloxystyrene, p-isoamyloxystyrene, 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-
Phenyloxystyrene, 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-ter
t-butoxyphenyloxy) styrene, p-benzyloxystyrene, p- (4-methylbenzyloxy) styrene, p-methoxymethoxystyrene, p- (1-ethoxyethoxy) styrene, p- (2-tetrahydropyranyloxy) ) Styrene, p-acetoxystyrene, p
-(Tert-butylcarbonyloxy) styrene, p
-Benzyloxycarbonyloxystyrene, p-methoxycarbonyloxystyrene, p- (tert-butoxycarbonyloxy) styrene, p-trimethylsilyloxystyrene, p-tert-butyldimethylsilyloxystyrene, m-nitrostyrene and the like. Further, the position of the substituent of the above substituted styrene is ortho,
It may be at any position of meta and para.

Further, examples of styrene derivatives of formula (I) (Ia) (Ib) having two or more substituents 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, 3,4-dimethylstyrene, 3,5-dimethylstyrene 2,3-dimethoxystyrene, 2,4-dimethoxystyrene, 2,5
-Dimethoxystyrene, 2,6-dimethoxystyrene,
3,4-dimethoxystyrene, 3,5-dimethoxystyrene, 2,3-methylenedioxystyrene, 3,4-methylenedioxystyrene, 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,
It may be 3,5-bis (trifluoromethyl) styrene. Furthermore, the styrene derivative is α of styrene.
And β-substituted styrene derivatives, for example α
-Methylstyrene, α-methyl-m-chlorostyrene,
α-ethylstyrene, α-trimethylsilyloxystyrene, α-methoxystyrene, α-chlorostyrene, β
It may be methyl styrene, β-methoxystyrene, β-chlorostyrene, β, β-dimethylstyrene, β, β-dichlorostyrene, α, β-dimethylstyrene, β-nitrostyrene.

The anthrone used as the polymerization inhibitor in the method of the present invention is a compound represented by the following formula (II).

[Chemical 7]

This anthrone is a known compound,
Known methods (for example, J. Chem. Soc.
53-page 354 (1970)), or a commercially available product.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is carried out as follows. That is, the polymerization inhibitor anthrone is added immediately after the production of styrene or a styrene derivative to be distilled. After this, a distillation operation may be performed.

The general formula (II) used in the method of the present invention
The amount of the anthrone of the formula (I) to be distilled is the substituent (R, X ₁ , X ₂ ) of the styrene or styrene derivative.
And X ₃ ) and the number thereof, the distillation temperature and the distillation pressure and the like, and are experimentally determined, but generally 10 to 100 relative to the styrene or styrene derivative of the general formula (I) to be distilled. 1,000 ppm, preferably in the range of 100 to 10,000 ppm. The distillation temperature is usually 20 to 200 ° C., preferably 40 to 150.
The temperature is ° C. Further, the distillation of styrene or a styrene derivative is usually carried out under reduced pressure, and usually, the distillation is performed at a pressure of 0.
0001 to 500 mmHg, preferably 0.0001 to
It is carried out under a pressure of 100 mmHg.

[0018]

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 In a four-diameter flask equipped with a distillation condenser, a thermometer and a stirrer, 100 g of PTBST (p-tert-butoxystyrene) immediately after being synthesized by the method of Japanese Patent Publication No. 4-71896 was used to inhibit polymerization. 0.05g of antron as an agent
(500 ppm concentration) was added to the mixture. This mixed solution was distilled in a flask at 130 ° C. under a reduced pressure of 5 mmHg for 48 hours while stirring. By this distillation step, 95.0 g of PTBST was distilled from the flask. At the bottom of the flask, 5.0 g of highly viscous liquid substance remained without being distilled. Distill from the flask,
The recovery rate (%) of PTBST that could be recovered was calculated by the following formula.

[0020]

[Equation 1]

Example 2 MTB in place of the distilled PTBST used in Example 1
The same distillation step as in Example 1 was operated except that ST (synthesized by the method described in JP-A-2-160739) was used. The results are shown in Table 1.

Example 3 In place of the distilled PTBST used in Example 1, p-acetoxystyrene (J. Org. Chem. Vol. 52) was used.
The same distillation step as in Example 1 was carried out except that the one synthesized by the method described on pages 422 to 424 (1987) was used. The results are shown in Table 1.

Example 4 3,4 in place of the distilled PTBST used in Example 1
-The same distillation step as in Example 1 was operated except that dimethoxystyrene (synthesized by the method described in JP-A-61-212526) was used. The results are shown in Table 1.

Example 5 In place of the distilled PTBST used in Example 1, α-methyl-m-chlorostyrene (JP-A-61-212526).
(Synthesized by the method described in the publication), except that
The same distillation process as in Example 1 was operated. The results are shown in Table 1.
Shown in.

Comparative Example 1 A distillation process was carried out in the same manner as in Example 1 except that the known polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt was used in place of the anthrone used as the polymerization inhibitor in Example 1. Operated. The results are shown in Table 1.

Comparative Example 2 The distillation step was operated in the same manner as in Example 2 except that the known polymerization inhibitor p-tert-butylcatechol was used in place of the anthrone used as the polymerization inhibitor in Example 2. . The results are shown in Table 1.

Comparative Example 3 A distillation step was carried out in the same manner as in Example 3 except that the known polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt was used in place of the anthrone used as the polymerization inhibitor in Example 3. Operated. The results are shown in Table 1.

Comparative Example 4 The distillation step was performed in the same manner as in Example 3 except that the known polymerization inhibitor p-tert-butylcatechol was used in place of the anthrone used as the polymerization inhibitor in Example 3. . The results are shown in Table 1.

Comparative Example 5 The distillation step was carried out in the same manner as in Example 4 except that the known polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt was used in place of the anthrone used as the polymerization inhibitor in Example 4. Operated. The results are shown in Table 1.

Comparative Example 6 The distillation step was operated in the same manner as in Example 4 except that the known polymerization inhibitor p-tert-butylcatechol was used in place of the anthrone used as the polymerization inhibitor in Example 4. . The results are shown in Table 1.

Comparative Example 7 A distillation step was carried out in the same manner as in Example 5 except that the known polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt was used in place of the anthrone used as the polymerization inhibitor in Example 5. Operated. The results are shown in Table 1.

Comparative Example 8 The distillation step was operated in the same manner as in Example 5 except that the known polymerization inhibitor p-tert-butylcatechol was used in place of the anthrone used as the polymerization inhibitor in Example 5. . The results are shown in Table 1.

[0033]

[Table 1]

[0034]

When the present invention is carried out, the following effects are brought about. 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 distillation method of styrene or styrene derivative of the present invention solves the conventional problems and is highly useful as an industrial method.

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Claims (5)

[Claims] 1. A distillation method for styrene or a styrene derivative, which comprises adding anthrone as a polymerization inhibitor to styrene or a styrene derivative, and distilling the styrene or styrene derivative in the presence of the polymerization inhibitor. 2. The styrene or styrene derivative to be distilled is represented by the following general formula (I): (In the formula, R represents 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. Group, aroyl group, especially benzoyl group, alkoxycarbonyl group, arylalkoxycarbonyl group, alkoxy group, haloalkoxy group, aryloxy group, aralkyloxy group, alkoxyalkyloxy group, alkanoyloxy group, alkoxycarbonyloxy group, aralkyloxycarbonyl Represents an oxy group or an alkylsilyloxy group, n is 0 or an integer from 1 to 5, and when n is 2 or more, R may be the same or different, and further, X ₁ , X ₂ , X ₃ is the same or different, water Atom, an alkyl group, wherein the alkoxy group is a compound represented by a halogen atom, an alkyl silyl group or a nitro group), a distillation method according to claim 1. 3. A styrene derivative to be distilled is represented by the following general formula (Ia): (In the formula, R ′ represents an alkyl group, a haloalkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, an alkanoyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group, and n is 1 to 5 Is an integer, and when n is 2 or more, R ′ may be the same or different, and further, X ₁ , X ₂ , X
₃ are the same or different and each is a hydrogen atom, an alkyl group,
An oxystyrene derivative represented by an alkoxy group, a halogen atom, an alkylsilyloxy group or a nitro group), the distillation method according to claim 1. 4. The styrene derivative to be distilled is represented by the following general formula (Ib): (In the formula, R '' represents an alkyl group, a haloalkyl group, an aryl group, particularly a phenyl group, an aralkyl group, particularly a benzyl group, an alkoxyalkyl group, an alkanoyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or an alkylsilyl group. It is an oxystyrene derivative represented by (shown), The distillation method of Claim 1 characterized by the above-mentioned. 5. The styrene derivative to be distilled is tert-
The method according to claim 1, wherein the distillation method is butoxystyrene.