JP3900809B2 - Method for distillation of oxystyrene derivatives - Google Patents

Description

【００２７】
実施例２〜実施例４
実施例１で使用したＮ−ニトロソフェニルヒドロキシルアミンアルミニウム塩に代えて、表１に示した重合禁止剤を所定量用いた以外は、実施例１に準じてＰＴＢＳを蒸留回収した。これらの結果を表１に示した。
【００２８】
実施例５
実施例１で使用したＰＴＢＳに代えてＭＴＢＳを用いた以外は、実施例１に準じてＭＴＢＳを蒸留回収した。これらの結果を表１に示した。
【００２９】
実施例６
実施例１で使用したＰＴＢＳに代えてＰＡＣＳを用い１２０℃、３ｍｍＨｇの蒸留条件及び蒸留液中にキャピラリーを通じて空気を導入した以外は、実施例１に準じてＰＡＣＳを蒸留回収した。これらの結果を表１に示した。
【００３０】
実施例７
実施例１で使用したエポキシ化合物を低分子量ビスフェノールＡ型エポキシ樹脂（平均分子量４００）に代えた以外は、実施例１に準じてＰＴＢＳを蒸留回収した。これらの結果を表１に示した。
【００３１】
比較例１
実施例１のエポキシ化合物を使用しなかった以外は、実施例１に準じてＰＴＢＳを蒸留回収した。これらの結果を表１に示した。
【００３２】
比較例２〜比較例５
実施例１のエポキシ化合物を使用せず、使用したＮ−ニトロソフェニルヒドロキシルアミンアルミニウム塩に代えて、表１に示した重合禁止剤を所定量用いた以外は、実施例１に準じてＰＴＢＳを蒸留回収した。これらの結果を表１に示した。
【００３３】
【発明の効果】
以上の説明から明らかなように、本発明の方法によれば、オキシスチレン誘導体の分解や重合が抑制され、なおかつ重合禁止剤であるニトロソ化合物やニトロ化合物の分解着色物の製品混入が抑制され、着色の抑制された高品質のオキシスチレン誘導体を高い回収率で蒸留可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for distilling an oxystyrene derivative useful as a raw material for medical and agricultural chemicals, functional polymers and the like. For example, p-tert-butoxystyrene (hereinafter abbreviated as PTBS) and p-acetoxystyrene (hereinafter abbreviated as PACS) are known to be extremely useful as resist materials used for VLSI applications and the like. (Japanese Patent Laid-Open Nos. 59-199705, 3-277608, and 6-266112) and m-tert-butoxystyrene (hereinafter abbreviated as MTBS) are highly functional. It is known to be useful as an intermediate raw material for molecules, medicines and agricultural chemicals (Japanese Patent Laid-Open No. 2-16039).
[0002]
[Prior art]
It is known that oxystyrene derivatives such as PTBS, PACS and MTBS are generally decomposed and polymerized by the presence of light, heat and acid.
[0003]
A tert-butoxystyrene such as PTBS or MTBS is obtained by reacting halostyrene with magnesium to form a Grignard reagent and then reacting with perbenzoic acid-tert-butyl ester (Japanese Patent Laid-Open No. 59-199705), tert- It is obtained by reacting butoxyhalobenzene with magnesium to give a Grignard reagent and then reacting it with a vinyl halide such as vinyl chloride or vinyl bromide (Japanese Patent Publication No. 4-71896, JP-A-2-160739). It is done. Acetoxystyrene such as PACS can be obtained by a method obtained by reacting acetoxybenzaldehyde with dibromomethane (JP-A-8-157410).
[0004]
As for the production methods of these oxystyrene derivatives, in any case, a distillation operation is usually performed in order to separate and recover the product. However, as described above, these oxystyrene derivatives have a problem that they are decomposed during distillation by light, heat and acid, or polymerized to form a polymer substance, resulting in a significant decrease in product yield. Furthermore, in most cases, the decomposition products are mixed in the product fraction and separated from the oxystyrene derivative, and it is difficult to obtain a high-quality product. In addition, the high-viscosity polymeric substance that is generated causes various troubles in the distillation kettle and the distillation column, and places a great load on the distillation apparatus and operation.
[0005]
Therefore, in order to avoid such a problem in the distillation process, a method of performing a distillation operation in the presence of various polymerization inhibitors has been used so far in order to suppress polymerization. However, the fact is that no special method has been taken to suppress decomposition.
[0006]
In the polymerization inhibition, quinones, phenols, nitrosophenols and nitrophenols are known as representative ones. For example, with tert-butoxystyrene such as PTBS and MTBS, distillation is performed in the presence of p-tert-butylcatechol (JP-B-4-71896, JP-A-2-160739), and PACS. In acetoxystyrene, a method of performing distillation in the presence of 2-tert-butylhydroquinone (JP-A-8-157410) is disclosed, but these polymerization inhibitors are used under low temperature and short time distillation conditions. Although a certain degree of polymerization suppression effect is recognized, in addition to the problem that sufficient polymerization suppression effect cannot be maintained at high temperature and long-time distillation at an industrial level, and in addition, there is no effect on decomposition and the product yield is reduced. The production of high-viscosity polymer substances clogs the distillation tower and piping, and decomposed products are mixed into the main fraction, resulting in a low-quality product. There is a problem such as that can not be obtained.
[0007]
On the other hand, nitroso compounds and nitro compounds typified by nitrosophenols and nitrophenols have excellent polymerization inhibitory effects, but they are easily decomposed and modified during distillation at high temperature and long time distillation, and produced. There are also problems such as degradation products and colored products mixed into the main fraction, leading to degradation of product quality. Thus, the conventional methods have many problems and are satisfactory as a distillation method for oxystyrene derivatives. is not.
[0008]
[Problems to be solved by the invention]
This invention is made | formed in view of said subject, The objective is to provide the distillation method of the oxystyrene derivative which was not satisfied with the conventional method. That is, without impairing the polymerization inhibitory effect of the polymerization inhibitor nitroso compound and nitro compound, the conventional problems were solved by suppressing the decomposition and coloring of the oxystyrene derivative and the polymerization inhibitor, and coloring was suppressed. An object of the present invention is to provide an economical distillation method for obtaining high-quality oxystyrene derivatives such as PTBS, PACS, and MTBS at a high recovery rate.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the conventional problems, the present inventors have found that nitroso compounds and / or nitro compounds as decomposition inhibitors and decomposition and products in the distillation process of oxystyrene derivatives such as PTBS, PACS, and MTBS By coexisting with an epoxy compound as a coloring inhibitor, polymerization and decomposition of oxystyrene derivatives such as PTBS, PACS, and MTBS can be suppressed, and further, high-quality products with suppressed coloring can be distilled at a high recovery rate. As a result, the present invention has been completed.
[0010]
That is, the present invention is a method for distilling an oxystyrene derivative, wherein an epoxy compound is allowed to coexist when the oxystyrene derivative is distilled in the presence of a nitroso compound and / or a nitro compound.
[0011]
Hereinafter, the present invention will be described in detail.
[0012]
The oxystyrene derivative represented by the general formula (1) used in the present invention is a hydroxyl group of hydroxystyrene having an alkyl group, an aryl group, an arylalkyl group, an alkoxyalkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylsilyl group. A group protected by, for example, p-methoxystyrene, m-methoxystyrene, p-ethoxystyrene, m-ethoxystyrene, pn-propoxystyrene, mn-propoxystyrene, pi-propoxy Styrene, mi-propoxystyrene, pn-butoxystyrene, mn-butoxystyrene, pi-butoxystyrene, mi-butoxystyrene, p-tert-butoxystyrene, m-tert-butoxystyrene , Pn-pentyloxystyrene, -N-pentyloxystyrene, pi-pentyloxystyrene, mi-pentyloxystyrene, p-tert-amyloxystyrene, p-tert-amyloxystyrene, p-cyclopropylmethyloxystyrene, m-cyclo Alkoxystyrenes such as propylmethyloxystyrene, p-cyclohexyloxystyrene, m-cyclohexyloxystyrene, p-phenyloxystyrene, m-phenyloxystyrene, p- (4-methylphenyl) oxystyrene, m- (4- Methylphenyl) oxystyrene, p- (2-methylphenyl) oxystyrene, m- (2-methylphenyl) oxystyrene, p- (4-methoxyphenyl) oxystyrene, m- (4-methoxyphenyl) oxystyrene, p- (2-Met Siphenyl) oxystyrene, m- (2-methoxyphenyl) oxystyrene, p- (4-ethoxyphenyl) oxystyrene, m- (4-ethoxyphenyl) oxystyrene, p- (2-ethoxyphenyl) oxystyrene, m -(2-ethoxyphenyl) oxystyrene, p- (4-tert-butoxyphenyl) oxystyrene, m- (4-tert-butoxyphenyl) oxystyrene, p- (2-tert-butoxyphenyl) oxystyrene, m Aryloxystyrenes such as-(2-tert-butoxyphenyl) oxystyrene, p-benzyloxystyrene, m-benzyloxystyrene, p- (4-methylphenyl) methoxystyrene, m- (4-methylphenyl) methoxy Arylalkyloxystyrene such as styrene , P-methoxymethoxystyrene, m-methoxymethoxystyrene, p-ethoxyethoxystyrene, m-ethoxyethoxystyrene, p- (2-tetrahydropyranyl) oxystyrene, m- (2-tetrahydropyranyl) oxystyrene Alkoxyalkyloxystyrenes such as p-acetoxystyrene, m-acetoxystyrene, p-tert-butylcarbonyloxystyrene, alkylcarbonyloxystyrenes such as m-tert-butylcarbonyloxystyrene, p-methoxycarbonyloxystyrene, m-methoxycarbonyloxystyrene, p-benzyloxycarbonyloxystyrene, m-benzyloxycarbonyloxystyrene, p-tert-butoxycarbonyloxystyrene, m-tert-butoxy Alkoxycarbonyloxystyrenes such as carbonyloxystyrene, alkylsilyloxystyrenes such as p-trimethylsilyloxystyrene, m-trimethylsilyloxystyrene, p-tert-butyldimethylsilyloxystyrene, m-tert-butyldimethylsilyloxystyrene, etc. Is mentioned.
[0013]
These are not particularly limited, but p-tert-butoxystyrene, m-tert-butoxystyrene, p-acetoxystyrene, m-acetoxystyrene, p-ethoxyethoxystyrene, m-ethoxyethoxystyrene and the like are preferably used. .
[0014]
In the method of the present invention, the epoxy compound used as a decomposition and coloring inhibitor refers to an epoxy compound containing an epoxy group in the structural formula. Examples of the epoxy compound include a low molecular weight epoxy resin having a diglycidyl ether structure of bisphenol A, a low molecular weight novolac epoxy resin having a diglycidyl ether structure of bisphenol F, and a low molecular weight polyhydroxybenzene having a diglycidyl ether structure of resorcinol. Epoxy resin, low molecular weight oxycarboxylic acid epoxy resin with diglycidyl ether structure of oxybenzoic acid, low molecular weight aromatic dicarboxylic acid epoxy resin with diglycidyl ether structure of phthalic acid, cyclohexene carboxylic acid cycloaliphatic epoxy resin And cyclic acetal-based epoxy resins.
[0015]
Of these, the use of cyclohexene carboxylic acid-based cycloaliphatic epoxy resins is preferred in consideration of decomposition, coloring suppression ability and ease of handling.
[0016]
It is estimated that the decomposition of the oxystyrene, the polymerization inhibitor, and the distillation of the colored product are suppressed in order to trap the acid and the colored product generated by this epoxy compound. The amount added is preferably 0.1% to 10% by weight, more preferably 0.5% to A range of 3% by weight is selected.
[0017]
In the method of the present invention, the nitroso compound used as a polymerization inhibitor means a compound containing a nitroso group in the structural formula. Examples of the nitroso compound include nitrosobenzene, nitrosotoluene, p-nitrosophenol, nitrosoresorcinol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol and other nitroso aromatic hydrocarbons, N-nitrosodiphenylamine, N- Examples include N-nitroso such as nitroso-N-methylaniline, N-nitroso-N-phenylaniline, N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine salts (metal salts, ammonium salts, etc.).
[0018]
In the method of the present invention, the nitro compound used as a polymerization inhibitor means one containing a nitro group in the structural formula. Examples of the nitro compound include o-, m-, p-dinitrobenzene, 2,4-dinitrochlorobenzene, 1,5-dinitronaphthalene, 2,4-dinitro-1-naphthol, 2,4-dinitrophenol, 2, Examples include nitroaromatic compounds such as 5-dinitrophenol, 2,4-dinitro-6-sec-butyl-phenol, 4,6-dinitro-o-cresol, 1,3,5-trinitrobenzene.
[0019]
Of these, N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, 2,4-dinitrophenol, 2,4- The use of 5-dinitrophenol is preferred.
[0020]
In the method of the present invention, the oxystyrene derivative is distilled in the presence of a nitroso compound and / or a nitro compound, and the addition amount of a polymerization inhibitor such as a nitroso compound or a nitro compound is considered in view of its effect and economy. The total amount of the oxystyrene derivative is preferably 1 ppm to 10 wt%, more preferably 100 ppm to 10000 ppm.
[0021]
In the method of the present invention, the distillation temperature of the oxystyrene derivative containing an epoxy compound and a polymerization inhibitor is not particularly limited, but is usually in the range of 20 to 200 ° C, and preferably 50 to 150 ° C. When the distillation temperature is within this range, the effects of decomposition, coloration inhibition and polymerization inhibition are sufficiently exhibited. Moreover, this distillation is normally implemented under reduced pressure and the range of 0.1-200 mmHg is chosen as a pressure. Furthermore, in the main distillation, the distillation may be carried out under an airless condition not accompanied by an air flow or an aired condition where an air current such as nitrogen or air is accompanied.
[0022]
In the method of the present invention, other polymerization inhibitors such as p-tert-butylcatechol, hydroquinone, p-methoxyphenol, phenothiazine and the like can coexist as desired in order to further improve the polymerization inhibition effect. .
[0023]
【Example】
EXAMPLES The method of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0024]
Example 1
In a 1000 ml flask, 800 g of PTBS and (3 ′, 4′-epoxycyclohexyl) methyl, 3,4-epoxycyclohexylcarboxylate as an epoxy compound <trade name Celoxide 2021; manufactured by Daicel Chemical Industries, Ltd.> 24.0 g, polymerization prohibited As an agent, 4.0 g of N-nitrosophenylhydroxylamine aluminum salt was added. Next, a reflux condenser was attached to this flask, and PTBS was recovered by distillation over 30 hours while adjusting the reflux ratio under the conditions of 120 ° C. and 5 mmHg, and the recovery rate was also determined. At this time, nitrogen was introduced into the liquid through a capillary.
[0025]
The purity of the recovered PTBS was analyzed by gas chromatography, and the degree of coloring was measured by comparison with a standard APHA solution according to the JIS-K-0071 (1999 edition) test method. Moreover, the residual in a flask was analyzed with the liquid chromatography, and the yield of the polymer was calculated | required. These results are shown in Table 1.
[0026]
[Table 1]

[0027]
Example 2 to Example 4
In place of the N-nitrosophenylhydroxylamine aluminum salt used in Example 1, PTBS was recovered by distillation according to Example 1 except that a predetermined amount of the polymerization inhibitor shown in Table 1 was used. These results are shown in Table 1.
[0028]
Example 5
MTBS was recovered by distillation according to Example 1 except that MTBS was used instead of PTBS used in Example 1. These results are shown in Table 1.
[0029]
Example 6
PACS was recovered by distillation according to Example 1 except that PACS was used in place of PTBS used in Example 1 and 120 ° C., 3 mmHg distillation conditions and air was introduced into the distillate through a capillary. These results are shown in Table 1.
[0030]
Example 7
PTBS was distilled and recovered in the same manner as in Example 1 except that the epoxy compound used in Example 1 was replaced with a low molecular weight bisphenol A type epoxy resin (average molecular weight 400). These results are shown in Table 1.
[0031]
Comparative Example 1
PTBS was recovered by distillation according to Example 1 except that the epoxy compound of Example 1 was not used. These results are shown in Table 1.
[0032]
Comparative Example 2 to Comparative Example 5
PTBS was distilled according to Example 1 except that the epoxy compound of Example 1 was not used, and instead of the used N-nitrosophenylhydroxylamine aluminum salt, a predetermined amount of the polymerization inhibitor shown in Table 1 was used. It was collected. These results are shown in Table 1.
[0033]
【The invention's effect】
As is clear from the above description, according to the method of the present invention, decomposition and polymerization of the oxystyrene derivative are suppressed, and further, mixing of the product of the nitroso compound that is a polymerization inhibitor or a decomposition colored product of the nitro compound is suppressed, A high-quality oxystyrene derivative with suppressed coloring can be distilled at a high recovery rate.

Claims (10)

The following general formula (1)

(Wherein R represents an alkyl group, an aryl group, an arylalkyl group, an alkoxyalkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an alkylsilyl group) and the presence of a nitroso compound and / or a nitro compound. A method for distilling an oxystyrene derivative, wherein an epoxy compound is allowed to coexist when distilling down. The method for distilling an oxystyrene derivative according to claim 1, wherein the oxystyrene derivative is tert-butoxystyrene represented by the following general formula (2).

The method for distilling an oxystyrene derivative according to claim 1, wherein the oxystyrene derivative is acetoxystyrene represented by the following general formula (3).

The method for distilling an oxystyrene derivative according to any one of claims 1 to 3, wherein the epoxy compound is a cycloaliphatic epoxy resin. The method for distilling an oxystyrene derivative according to any one of claims 1 to 4, wherein the nitroso compound is N-nitrosophenylhydroxylamine and / or a salt thereof. The method for distilling an oxystyrene derivative according to any one of claims 1 to 4, wherein the nitro compound is dinitrophenol. The following general formula (1), comprising a nitroso compound and / or a nitro compound, and an epoxy compound

(Wherein R represents an alkyl group, an aryl group, an arylalkyl group, an alkoxyalkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an alkylsilyl group), a polymerization inhibitor for oxystyrene derivatives. The polymerization inhibitor for oxystyrene derivatives according to claim 7 , wherein the nitroso compound is N-nitrosophenylhydroxylamine and / or a salt thereof. The polymerization inhibitor for oxystyrene derivatives according to claim 7 , wherein the nitro compound is dinitrophenol. The polymerization inhibitor for oxystyrene derivatives according to claim 7 , wherein the epoxy compound is a cycloaliphatic epoxy resin.