JP3879775B2 - Method for distillation of oxystyrene derivatives - Google Patents

Description

  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, para-tertiary-butoxystyrene (hereinafter, p-tertiary-butoxystyrene is abbreviated as “PTBS”), para-acetoxystyrene (hereinafter, p-acetoxystyrene is abbreviated as “PACS”) are: It is known that it is extremely useful as a resist material used for VLSI applications (JP 59-199705 A, JP 3-277608 A, JP 6-266112 A), and , Meta-tertiary-butoxystyrene (hereinafter, m-tertiary-butoxystyrene is abbreviated as “MTBS”) is known to be useful as an intermediate raw material for functional polymers, medicines and agricultural chemicals. (Japanese Patent Laid-Open No. 2-160739).

  It is known that oxystyrene derivatives such as PTBS, PACS, and MTBS are generally polymerized by light or heat. For example, tertiary-butoxystyrene such as PTBS and MTBS is obtained by reacting halostyrene with magnesium to form a Grignard reagent and then reacting with perbenzoic acid-tertiary butyl ester (Japanese Patent Laid-Open No. 59-199705). No. 4-7896, JP-A-2-71896, and a method obtained by reacting tertiary-butoxyhalobenzene with magnesium to form a Grignard reagent and then reacting with vinyl halide such as vinyl chloride or vinyl bromide. No. 160739) and the like. Acetoxystyrene such as PACS can be obtained by a method obtained by reacting acetoxybenzaldehyde with dibromomethane (JP-A-8-157410).

  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, since these oxystyrene derivatives are polymerized by light or heat to form a polymer substance as described above, there is a problem that the product yield is remarkably lowered. Further, since a highly viscous polymer substance is generated in the distillation kettle and the distillation column, various troubles are caused. Therefore, in order to avoid such a polymerization trouble in the distillation step, a method of performing a distillation operation in the presence of a polymerization inhibitor has been taken so far. For example, in tertiary-butoxystyrene such as PTBS and MTBS, distillation is performed in the presence of p-tertiary-butylcatechol (Japanese Patent Publication No. 4-71896, Japanese Patent Laid-Open No. 2-16039). In addition, a method of performing distillation in the presence of 2-tertiary-butylhydroquinone in acetoxystyrene such as PACS (JP-A-8-157410) is disclosed.

  However, these polymerization inhibitors do not exhibit a sufficient effect of suppressing polymer formation under heating conditions in the distillation process, and in addition to the problem that the product yield is reduced, Troubles such as blockage of piping were caused, and it was not satisfactory as a distillation method for oxystyrene derivatives.

  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, an object of the present invention is to provide an economical distillation method that solves the conventional problems and produces an oxystyrene derivative such as PTBS, PACS, or MTBS with little recovery of polymer and high recovery.

  As a result of intensive studies to solve the conventional problems, the present inventors have added a nitroso compound and / or a nitro compound as a polymerization inhibitor in a distillation step of oxystyrene derivatives such as PTBS, PACS, and MTBS. Thus, it has been found that oxystyrene derivatives such as PTBS, PACS, and MTBS can be distilled at a high recovery rate without substantially producing a polymer substance, and the present invention has been completed.

That is, in the distillation of an oxystyrene derivative, the present invention adds N-nitrosophenylhydroxylamine and / or its aluminum salt or ammonium salt as a nitroso compound and / or dinitrophenol as a nitro compound as a polymerization inhibitor. This is a characteristic distillation method for oxystyrene derivatives.

  Hereinafter, the present invention will be described in detail.

  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, A substance substituted with an alkylsilyl group, for example, p-methoxystyrene, m-methoxystyrene, p-ethoxystyrene, m-ethoxystyrene, pn-propoxystyrene, mn-propoxystyrene, pi -Propoxystyrene, mi-propoxystyrene, pn-butoxystyrene, mn-butoxystyrene, pi-butoxystyrene, mi-butoxystyrene, p-tertiary-butoxystyrene (PTBS) , M-tertiary-butoxystyrene (MTBS), pn Pentyloxystyrene, mn-pentyloxystyrene, pi-pentyloxystyrene, mi-pentyloxystyrene, p-tertiary-amyloxystyrene, p-tertiary-amyloxystyrene, p- Alkoxystyrenes such as cyclopropylmethyloxystyrene, m-cyclopropylmethyloxystyrene, 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) oxys Len, p- (2-methoxyphenyl) oxystyrene, m- (2-methoxyphenyl) oxystyrene, p- (4-ethoxyphenyl) oxystyrene, m- (4-ethoxyphenyl) oxystyrene, p- (2 -Ethoxyphenyl) oxystyrene, m- (2-ethoxyphenyl) oxystyrene, p- (4-tertiary-butoxyphenyl) oxystyrene, m- (4-tertiary-butoxyphenyl) oxystyrene, p- Aryloxystyrenes such as (2-tertiary-butoxyphenyl) oxystyrene, m- (2-tertiary-butoxyphenyl) oxystyrene, p-benzyloxystyrene, m-benzyloxystyrene, p- (4 -Methylphenyl) methoxystyrene, m- (4-methylphenyl) methoxystyrene, etc. aryl alcohols Alkoxyalkyloxystyrenes such as killyoxystyrenes, p-methoxymethoxystyrene, m-methoxymethoxystyrene, p- (2-tetrahydropyranyl) oxystyrene, m- (2-tetrahydropyranyl) oxystyrene, p- Alkylcarbonyloxystyrenes such as acetoxystyrene (PACS), m-acetoxystyrene, p-acetoxystyrene, p-tertiary-butylcarbonyloxystyrene, m-tertiary-butylcarbonyloxystyrene, p-methoxycarbonyloxy Styrene, m-methoxycarbonyloxystyrene, p-benzyloxycarbonyloxystyrene, m-benzyloxycarbonyloxystyrene, p-tertiary-butoxycarbonyloxystyrene, m-tertiary-butoxycarbonyloxy Alkoxycarbonyloxystyrenes such as styrene, p-trimethylsilyloxystyrene, m-trimethylsilyloxystyrene, p-tertiary-butyldimethylsilyloxystyrene, alkyl-silyloxystyrene such as m-tertiary-butyldimethylsilyloxystyrene And the like.

  The addition amount of the nitroso compound and / or the nitro compound in the method of the present invention is selected in the range of 1 to 100,000 ppm, preferably 100 to 10,000 ppm with respect to the oxystyrene derivative. When the addition amount is less than 1 ppm, the polymerization inhibition effect is not sufficiently exhibited. On the other hand, if it exceeds 100000 ppm, the effect is not improved with respect to the added amount, but it is rather economically disadvantageous.

  In the method of the present invention, the distillation temperature of the oxystyrene derivative containing the polymerization inhibitor is not particularly limited, but is usually in the range of 20 to 200 ° C, preferably 50 to 150 ° C. When the distillation temperature is within this range, the polymerization preventing effect is 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.

  In the method of the present invention, other polymerization inhibitors such as p-tertiary-butylcatechol, hydroquinone, p-methoxyphenol and the like can coexist as desired in order to further improve the polymerization prevention effect. .

  As is clear from the above description, according to the method of the present invention, it is possible to solve the conventional problems and to distill the oxystyrene derivative at a high recovery rate with almost no polymer substance. Become.

  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.

Example 1
To a 100 ml flask, 10 g of PTBS and 0.01 g of N-nitrosophenylhydroxylamine ammonium salt as a polymerization inhibitor were added. Next, a reflux condenser was attached to the flask, and the mixture was refluxed continuously at 120 ° C. and 5 mmHg for 16 hours. At this time, air was introduced into the liquid through a capillary.

  After the refluxing, PTBS in the flask was sampled and analyzed by liquid chromatography (column: GPC-2000), and the yield of the polymer was determined from the composition. The results are shown in Table 1.

実施例２〜１０
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ンモニウム塩に代えて、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に準じて還流を行い、それらの結果を表１にまとめて示した。

Examples 2-10
In place of the N-nitrosophenylhydroxylamine ammonium salt used in Example 1, a predetermined amount of the polymerization inhibitor shown in Table 1 was used, and refluxing was performed according to Example 1, and the results are shown in Table 1. Are summarized in

Example 11
Reflux was carried out according to Example 1 except that 10 g of MTBS was used instead of PTBS used in Example 1. After completion of the reflux, the MTBS in the flask was sampled and analyzed by liquid chromatography (column: GPC-2000), the polymer yield was determined from the composition, and the results are shown in Table 1.

Comparative Examples 1-4
In place of the N-nitrosophenylhydroxylamine ammonium salt used in Example 1, a predetermined amount of the polymerization inhibitor shown in Table 1 was used, and refluxing was performed according to Example 1, and the results are shown in Table 1. Are summarized in

Comparative Example 5
Reflux was carried out according to Example 1 except that 10 g of MTBS was used instead of PTBS used in Example 1 and 0.01 g of p-tertiary-butylcatechol was used as a polymerization inhibitor. After completion of the reflux, the MTBS in the flask was sampled and analyzed by liquid chromatography (column: GPC-2000), the polymer yield was determined from the composition, and the results are shown in Table 1.

Example 12
To a 100 ml flask, 10 g of PACS and 0.05 g of N-nitrosophenylhydroxylamine aluminum salt as a polymerization inhibitor were added. Next, a reflux condenser was attached to the flask, and the mixture was refluxed continuously at 120 ° C. and 4 mmHg for 16 hours. At this time, air was introduced into the liquid through a capillary.

  After completion of the reflux, the PACS in the flask was sampled and analyzed by liquid chromatography (column: GPC-2000), the polymer yield was determined from the composition, and the results are shown in Table 2.

実施例１３〜１８
実施例１２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２に示した重合禁止剤を所定量用いた以外は、実施例１２に準じて還流を行い、その結果を表２にまとめて示した。

Examples 13-18
Instead of the N-nitrosophenylhydroxylamine aluminum salt used in Example 12, a predetermined amount of the polymerization inhibitor shown in Table 2 was used, and refluxing was performed according to Example 12, and the results are shown in Table 2. Shown together.

Comparative Examples 6-10
Instead of the N-nitrosophenylhydroxylamine aluminum salt used in Example 12, a predetermined amount of the polymerization inhibitor shown in Table 2 was used, and refluxing was performed according to Example 12. The results are shown in Table 2. Are summarized in

Claims (3)

The following general formula (1)
(In the formula, R represents an alkyl group, an aryl group, an arylalkyl group, an alkoxyalkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an alkylsilyl group.)
N-nitrosophenylhydroxylamine and / or its aluminum or ammonium salt as a nitroso compound, which is added to inhibit polymerization of the oxystyrene derivative in the distillation of the oxystyrene derivative represented by A polymerization inhibitor comprising dinitrophenol as a nitro compound.

The polymerization inhibitor according to claim 1, wherein the oxystyrene derivative is tertiary-butoxystyrene represented by the following general formula (2).

The polymerization inhibitor according to claim 1, wherein the oxystyrene derivative is acetoxystyrene represented by the following general formula (3).