JP4479170B2 - Method for distillation of oxystyrene derivatives - Google Patents

Description

【化６】

以下、本発明を詳細に説明する。
【００１２】
本発明において使用される上記一般式（１）で表わされるオキシスチレン誘導体とは、ヒドロキシスチレンの水酸基がＲで保護されたものを言い、Ｒはアルキル基、アリール基、アリールアルキル基、アルコキシアルキル基、アルキルカルボニル基、アルコキシカルボニル基又はアルキルシリル基である。一般式（１）で表わされるオキシスチレン誘導体は、例えば、ｐ−メトキシスチレン、ｍ−メトキシスチレン、ｐ−エトキシスチレン、ｍ−エトキシスチレン、ｐ−ｎ−プロポキシスチレン、ｍ−ｎ−プロポキシスチレン、ｐ−ｉ−プロポキシスチレン、ｍ−ｉ−プロポキシスチレン、ｐ−ｎ−ブトキシスチレン、ｍ−ｎ−ブトキシスチレン、ｐ−ｉ−ブトキシスチレン、ｍ−ｉ−ブトキシスチレン、ｐ−ｔｅｒｔ−ブトキシスチレン、ｍ−ｔｅｒｔ−ブトキシスチレン、ｐ−ｎ−ペンチルオキシスチレン、ｍ−ｎ−ペンチルオキシスチレン、ｐ−ｉ−ペンチルオキシスチレン、ｍ−ｉ−ペンチルオキシスチレン、ｐ−ｔｅｒｔ−アミルオキシスチレン、ｐ−ｔｅｒｔ−アミルオキシスチレン、ｐ−シクロプロピルメチルオキシスチレン、ｍ−シクロプロピルメチルオキシスチレン、ｐ−シクロヘキシルオキシスチレン、ｍ−シクロヘキシルオキシスチレン等のアルコキシスチレン類、ｐ−フェニルオキシスチレン、ｍ−フェニルオキシスチレン、ｐ−（４−メチルフェニル）オキシスチレン、ｍ−（４−メチルフェニル）オキシスチレン、ｐ−（２−メチルフェニル）オキシスチレン、ｍ−（２−メチルフェニル）オキシスチレン、ｐ−（４−メトキシフェニル）オキシスチレン、ｍ−（４−メトキシフェニル）オキシスチレン、ｐ−（２−メトキシフェニル）オキシスチレン、ｍ−（２−メトキシフェニル）オキシスチレン、ｐ−（４−エトキシフェニル）オキシスチレン、ｍ−（４−エトキシフェニル）オキシスチレン、ｐ−（２−エトキシフェニル）オキシスチレン、ｍ−（２−エトキシフェニル）オキシスチレン、ｐ−（４−ｔｅｒｔ−ブトキシフェニル）オキシスチレン、ｍ−（４−ｔｅｒｔ−ブトキシフェニル）オキシスチレン、ｐ−（２−ｔｅｒｔ−ブトキシフェニル）オキシスチレン、ｍ−（２−ｔｅｒｔ−ブトキシフェニル）オキシスチレン等のアリールオキシスチレン類、ｐ−ベンジルオキシスチレン、ｍ−ベンジルオキシスチレン、ｐ−（４−メチルフェニル）メトキシスチレン、ｍ−（４−メチルフェニル）メトキシスチレン等のアリールアルキルオキシスチレン類、ｐ−メトキシメトキシスチレン、ｍ−メトキシメトキシスチレン、ｐ−エトキシエトキシスチレン、ｍ−エトキシエトキシスチレン、ｐ−（２−テトラヒドロピラニル）オキシスチレン、ｍ−（２−テトラヒドロピラニル）オキシスチレン等のアルコキシアルキルオキシスチレン類、ｐ−アセトキシスチレン、ｍ−アセトキシスチレン、ｐ−ｔｅｒｔ−ブチルカルボニルオキシスチレン、ｍ−ｔｅｒｔ−ブチルカルボニルオキシスチレン等のアルキルカルボニルオキシスチレン類、ｐ−メトキシカルボニルオキシスチレン、ｍ−メトキシカルボニルオキシスチレン、ｐ−ベンジロキシカルボニルオキシスチレン、ｍ−ベンジロキシカルボニルオキシスチレン、ｐ−ｔｅｒｔ−ブトキシカルボニルオキシスチレン、ｍ−ｔｅｒｔ−ブトキシカルボニルオキシスチレン等のアルコキシカルボニルオキシスチレン類、ｐ−トリメチルシリルオキシスチレン、ｍ−トリメチルシリルオキシスチレン、ｐ−ｔｅｒｔ−ブチルジメチルシリルオキシスチレン、ｍ−ｔｅｒｔ−ブチルジメチルシリルオキシスチレン等のアルキルシリルオキシスチレン類等が挙げられる。
【００１３】
これらは特に限定するものではないが、上記一般式（１）で表されるオキシスチレン誘導体の内、下記一般式（３）で表わされるｔｅｒｔ−ブトキシスチレン又は下記一般式（４）で表わされるアセトキシスチレンが好ましく用いられ、
【００１４】
【化７】

【化８】

例えば、ｐ−ｔｅｒｔ−ブトキシスチレン、ｍ−ｔｅｒｔ−ブトキシスチレン、ｐ−アセトキシスチレン、ｍ−アセトキシスチレン等が好ましく用いられる。
【００１５】
本発明の方法において、重合禁止剤として前記一般式（２）で表されるビスフェノール系化合物が用いられ、式中Ｘは、単結合、Ｃ₁〜Ｃ₂アルキレン、Ｃ₂〜Ｃ₅アルキリデン、Ｃ₅〜Ｃ₆シクロアルキリデン、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−を表す。Ｒ₁とＲ₂は水素原子、炭素数１〜１０のアルキル基、シクロアルキル基またはフェニル基であり、Ｒ₁とＲ₂は同じでも異なっていてもよい。また、ｍおよびｎは置換基数を表し、０〜４の整数である。
【００１６】
上記一般式（２）で表されるビスフェノール系化合物としては、例えば、２，２’−メチレン−ビス−（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレン−ビス−（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレン−ビス（６−アルファメチルベンジル−ｐ−クレゾール）、２，２’−メチレン−ビス−（４−メチル−６−シクロヘキシルフェノール）、４，４’−メチレン−ビス−（２，６−ジ−ｔｅｒｔ−ブチルフェノール）等のメチレンビスフェノール類、２，２’−エチリデン−ビス−（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−エチリデン−ビス−（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−エチリデンビスフェノール、４，４’−エチリデン−ビス−（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−エチリデン−ビス−（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４’−エチリデン−ビス−（２，６−ジメチルフェノール）等のエチリデンビスフェノール類、２，２’−イソプロピリデン−ビス−（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−イソプロピリデン−ビス−（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−イソプロピリデンビスフェノール、４，４’−イソプロピリデン−ビス−（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−イソプロピレデン−ビス−（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４’−イソプロピリデン−ビス−（２，６−ジメチルフェノール）等のプロピリデンビスフェノール類、４，４’−ブチリデン−ビス−（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−ブチリデン−ビス−（２，６−ジ−ｔｅｒｔ−ブチルフェノール）等のブチリデンビスフェノール類、４，４’−チオビス−（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−チオビス−（２，６−ジ−ｔｅｒｔ−ブチルフェノール）等のチオビスフェノール類、ビス−（ｐ−ヒドロキシフェニル）エーテル等のフェニルエーテル類、４，４’−ジヒドロキシベンゾフェノン等のベンゾフェノン類、ビス−（ｐ−ヒドロキシフェニル）スルホキシド等のビスフェニルスルホキシド類、ビス−（ｐ−ヒドロキシフェニル）スルホン等のビスフェニルスルホン類を挙げられる。
【００１７】
これらのうち、重合禁止能力及び入手の容易さを考慮すると、２，２’−メチレン−ビス−（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレン−ビス−（４−エチル−６−ｔｅｒｔ−ブチルフェノール）の使用が好ましい。
【００１８】
本発明の方法において、重合禁止剤としてビスフェノール系化合物とは別に、ニトロソ化合物及び／又はニトロ化合物を添加しても良い。
【００１９】
重合禁止剤として用いられるニトロソ化合物とは、構造式中にニトロソ基を含有するものを言う。ニトロソ化合物としては例えば、ニトロソベンゼン、ニトロソトルエン、ｐ−ニトロソフェノール、ニトロソレゾルシノール、１−ニトロソ−２−ナフトール、２−ニトロソ−１−ナフトール等のニトロソ芳香族炭化水素、Ｎ−ニトロソジフェニルアミン、Ｎ−ニトロソ−Ｎ−メチルアニリン、Ｎ−ニトロソ−Ｎ−フェニルアニリン、Ｎ−ニトロソフェニルヒドロキシルアミン、Ｎ−ニトロソフェニルヒドロキシルアミン塩（金属塩、アンモニウム塩等）等のＮ−ニトロソ類が挙げられる。
【００２０】
本発明の方法において、重合禁止剤として用いられるニトロ化合物とは、構造式中にニトロ基を含有するものを言う。ニトロ化合物としては例えば、ｏ−、ｍ−、ｐ−ジニトロベンゼン、２，４−ジニトロクロロベンゼン、１，５−ジニトロナフタレン、２，４−ジニトロ−１−ナフトール、２，４−ジニトロフェノール、２，５−ジニトロフェノール、２，４−ジニトロ−６−ｓｅｃ−ブチル−フェノール、４，６−ジニトロ−ｏ−クレゾール、１，３，５−トリニトロベンゼン等のニトロ芳香族化合物が挙げられる。
【００２１】
これらのうち、重合禁止能力及び入手の容易さを考慮すると、ニトロソ化合物としては、Ｎ−ニトロソフェニルヒドロキシルアミン及び／又はその塩、例えば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、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、ニトロ化合物としては、ジニトロフェノール、例えば２，４−ジニトロフェノール、２，５−ジニトロフェノールの使用が好ましい。
【００２２】
本発明の方法において、重合禁止剤の添加量は、その効果と経済性等を考慮すると、オキシスチレン誘導体に対し、ビスフェノール系化合物単独で、好ましくは１ｐｐｍ〜１０重量％、さらに好ましくは、１００ｐｐｍ〜１００００ｐｐｍの範囲が選ばれ、ビスフェノール系化合物とは別に、ニトロソ化合物、ニトロ化合物を添加する場合、総量で好ましくは１ｐｐｍ〜１０重量％、さらに好ましくは、１００ｐｐｍ〜１００００ｐｐｍの範囲が選ばれる。
【００２３】
本発明の方法において、重合禁止剤を含むオキシスチレン誘導体の蒸留温度は、特に制限はないが、通常、２０〜２００℃の範囲であり、好ましくは、５０〜１５０℃である。蒸留温度がこの範囲内であれば、重合抑制及び着色抑制効果が十分に発揮される。また、本蒸留は、通常、減圧下で実施され、圧力としては０．１〜２００ｍｍＨｇの範囲が選ばれる。更に、本蒸留においては、気流同伴を伴わない無気条件又は、窒素あるいは空気等の気流同伴を行う有気条件下のいずれで蒸留を実施しても良い。
【００２４】
本発明の方法においては、重合防止効果を更に向上させるために、所望に応じ、他の重合禁止剤、例えばｐ−ｔｅｒｔ−ブチルカテコール、ハイドロキノン、ｐ−メトキシフェノール、フェノチアジン等を共存させることができる。
【００２５】
【実施例】
以下に、本発明の方法を実施例により具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。
【００２６】
実施例１
１０００ｍｌフラスコに、ＰＴＢＳ８００ｇと重合禁止剤として２，２’−メチレン−ビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）４．０ｇを添加した。次にこのフラスコに還流コンデンサーを取り付けて、１２０℃、５ｍｍＨｇの条件で還流比を調整しながら３０時間かけて、ＰＴＢＳを蒸留回収し、回収率を求めた。なお、この際、液中にキャピラリーを通じて窒素を導入した。回収したＰＴＢＳの着色度合をＪＩＳ−Ｋ−００７１（１９９９年版）試験法に準じて標準ＡＰＨＡ液と比較測定した。結果を表１に示す。
【００２７】
実施例２〜４
実施例１で使用した２，２’−メチレン−ビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）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。結果をあわせて表１に示す。
【００２８】
実施例５
実施例１で使用したＰＴＢＳに代えてＭＴＢＳ８００ｇを用いた以外は、実施例１に準じてＭＴＢＳを蒸留回収した。結果をあわせて表１に示す。
【００２９】
実施例６
実施例１で使用したＰＴＢＳに代えてＭＴＢＳ８００ｇを用い、使用した２，２’−メチレン−ビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）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ＭＴＢＳを蒸留回収した。結果をあわせて表１に示す。
【００３０】
実施例７
実施例１で使用したＰＴＢＳに代えてＰＡＣＳ８００ｇを用いた以外は、実施例１に準じてＰＡＣＳを蒸留回収した。結果をあわせて表１に示す。
【００３１】
実施例８
実施例１で使用したＰＴＢＳに代えてＰＡＣＳ８００ｇを用い、使用した２，２’−メチレン−ビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）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ＰＡＣＳを蒸留回収した。結果をあわせて表１に示す。
【００３２】
比較例１〜３
実施例１で使用した２，２’−メチレン−ビス−（４−エチル−６−ｔ−ブチルフェノール）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。結果をあわせて表１に示す。
【００３３】
比較例４
実施例１で使用したＰＴＢＳに代えてＰＡＣＳ８００ｇを用い、使用した２，２’−メチレン−ビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）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ＰＡＣＳを蒸留回収した。結果をあわせて表１に示す。
【００３４】
【表１】

【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、従来の問題点を解決して、ポリマー状物質をほとんど生成することなく、なおかつ、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.
[0002]
[Prior art]
For example, p-tert-butoxystyrene (hereinafter abbreviated as PTBS) and p-acetoxystyrene (hereinafter abbreviated as PACS) are extremely useful as resist materials used for VLSI applications and the like. Known (for example, refer to Patent Documents 1 to 3), and m-tert-butoxystyrene (hereinafter abbreviated as MTBS) is useful as an intermediate material for functional polymers, medical pesticides and the like. It is known (for example, refer to Patent Document 4).
[0003]
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.
[0004]
A tert-butoxystyrene such as PTBS or MTBS is obtained by reacting halostyrene with magnesium to give a Grignard reagent and then reacting with perbenzoic acid-tert-butyl ester (see, for example, Patent Document 1), tert-butoxy. It is obtained by a method obtained by reacting halobenzene with magnesium to obtain a Grignard reagent and then reacting with vinyl halide such as vinyl chloride or vinyl bromide (for example, see Patent Documents 4 to 5). Further, acetoxystyrene such as PACS can be obtained by a method obtained by reacting acetoxybenzaldehyde with dibromomethane (for example, see Patent Document 6).
[0005]
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 the product yield is remarkably lowered by polymerization during distillation by light or heat to form a polymer substance. Furthermore, the high-viscosity polymeric substance produced causes various troubles in the distillation kettle and the distillation column, and places a great load on the distillation apparatus and operation.
[0006]
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. For example, with tert-butoxystyrene such as PTBS and MTBS, distillation is performed in the presence of p-tert-butylcatechol (see, for example, Patent Documents 4 to 5), or in the presence of a hydroxylamine derivative. A method (for example, see Patent Document 6) and a method for performing distillation in the presence of 2-tert-butylhydroquinone for acetoxystyrene such as PACS (for example, see Patent Document 7) are disclosed. Although a polymerization inhibitory effect is observed to a certain degree under low temperature and short distillation conditions, a sufficient polymerization inhibitory effect cannot be maintained at a high temperature and long distillation at an industrial level, resulting in a product yield. In addition to the problem of reduction, the generation of high-viscosity polymer-like substances causes troubles such as clogging of distillation towers and piping. Straining often. In addition, decomposition and modification are liable to occur during distillation, and there are also problems such as degradation products and colored products that are mixed into the main fraction, leading to a reduction in product quality. As described above, the conventional methods have many problems and are not satisfactory as a distillation method for oxystyrene derivatives.
[0007]
[Patent Document 1]
JP 59-199705 A [Patent Document 2]
JP-A-3-277608 [Patent Document 3]
JP-A-6-266112 [Patent Document 4]
Japanese Patent Laid-Open No. 2-160737 [Patent Document 5]
Japanese Patent Publication No. 4-71896 [Patent Document 6]
JP 2003-2856 A [Patent Document 7]
Japanese Patent Laid-Open No. 8-157410
[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, a distillation method that solves the conventional problems, has almost no polymer formation, and is excellent in economic efficiency to obtain high-quality oxystyrene derivatives such as PTBS, PACS, and MTBS with suppressed coloring. Is to provide.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the conventional problems, the present inventors have found that bisphenol represented by the following general formula (2) as a polymerization inhibitor in a distillation process of oxystyrene derivatives such as PTBS, PACS, and MTBS. By adding a bisphenol compound, and further adding a bisphenol compound and a nitroso compound and / or a nitro compound together, an oxystyrene derivative such as PTBS, PACS, or MTBS is substantially converted into a polymer substance. Furthermore, the present inventors have found that a high-quality product in which coloring is suppressed can be distilled at a high recovery rate without being produced, and the present invention has been completed.
[0010]
That is, the present invention provides an oxystyrene characterized by adding a bisphenol compound represented by the following general formula (2) as a polymerization inhibitor in distillation of the oxystyrene derivative represented by the following general formula (1): This is a distillation method for derivatives.
[0011]
[Chemical formula 5]

[Chemical 6]

Hereinafter, the present invention will be described in detail.
[0012]
The oxystyrene derivative represented by the general formula (1) used in the present invention refers to a hydroxyl group of hydroxystyrene protected with R, where R is an alkyl group, aryl group, arylalkyl group, alkoxyalkyl group. , An alkylcarbonyl group, an alkoxycarbonyl group or an alkylsilyl group. Examples of the oxystyrene derivative represented by the general formula (1) include p-methoxystyrene, m-methoxystyrene, p-ethoxystyrene, m-ethoxystyrene, pn-propoxystyrene, mn-propoxystyrene, p -I-propoxystyrene, mi-propoxystyrene, pn-butoxystyrene, mn-butoxystyrene, pi-butoxystyrene, mi-butoxystyrene, p-tert-butoxystyrene, m- tert-butoxystyrene, pn-pentyloxystyrene, mn-pentyloxystyrene, pi-pentyloxystyrene, mi-pentyloxystyrene, p-tert-amyloxystyrene, p-tert-amyl Oxystyrene, p-cyclopropylmethyloxystyrene, m Alkoxystyrenes such as 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) oxystyrene 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-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) methoxystyrene, etc. Arylalkyloxystyrenes, p-methoxymethoxystyrene, m-methoxymethoxystyrene, p-ethoxyethoxystyrene, m-ethoxyethoxystyrene, p- (2-tetrahydropyranyl) oxystyrene, m- (2-tetrahydropyrani) Le) Oki Alkoxyalkyloxystyrenes such as styrene, p-acetoxystyrene, m-acetoxystyrene, p-tert-butylcarbonyloxystyrene, alkylcarbonyloxystyrenes such as m-tert-butylcarbonyloxystyrene, p-methoxycarbonyloxystyrene Alkoxycarbonyloxystyrenes such as m-methoxycarbonyloxystyrene, p-benzyloxycarbonyloxystyrene, m-benzyloxycarbonyloxystyrene, p-tert-butoxycarbonyloxystyrene, m-tert-butoxycarbonyloxystyrene, p -Trimethylsilyloxystyrene, m-trimethylsilyloxystyrene, p-tert-butyldimethylsilyloxystyrene, m-tert-butyl Alkylsilyloxy styrene such as methyl silyloxy styrene.
[0013]
These are not particularly limited, but among the oxystyrene derivatives represented by the general formula (1), tert-butoxystyrene represented by the following general formula (3) or acetoxy represented by the following general formula (4) Styrene is preferably used,
[0014]
[Chemical 7]

[Chemical 8]

For example, p-tert-butoxystyrene, m-tert-butoxystyrene, p-acetoxystyrene, m-acetoxystyrene and the like are preferably used.
[0015]
In the method of the present invention, a bisphenol compound represented by the general formula (2) is used as a polymerization inhibitor, wherein X is a single bond, C ₁ -C ₂ alkylene, C ₂ -C ₅ alkylidene, C _{5 to} C ₆ cycloalkylidene, —O—, —CO—, —S—, —SO—, —SO ₂ — is represented. R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and R ₁ and R ₂ may be the same or different. Moreover, m and n represent the number of substituents and are integers of 0-4.
[0016]
Examples of the bisphenol compound represented by the general formula (2) include 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4 -Ethyl-6-tert-butylphenol), 2,2'-methylene-bis (6-alphamethylbenzyl-p-cresol), 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), Methylene bisphenols such as 4,4′-methylene-bis- (2,6-di-tert-butylphenol), 2,2′-ethylidene-bis- (4-methyl-6-tert-butylphenol), 2,2 '-Ethylidene-bis- (4-ethyl-6-tert-butylphenol), 4,4'-ethylidenebisphenol, 4,4'-ethylidene-bis- (3- Ethyl-6-tert-butylphenol), 4,4'-ethylidene-bis- (2,6-di-tert-butylphenol), 4,4'-ethylidene-bis- (2,6-dimethylphenol), etc. Bisphenols, 2,2'-isopropylidene-bis- (4-methyl-6-tert-butylphenol), 2,2'-isopropylidene-bis- (4-ethyl-6-tert-butylphenol), 4,4 '-Isopropylidenebisphenol, 4,4'-isopropylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-isopropylidene-bis- (2,6-di-tert-butylphenol), Propylidenebisphenols such as 4,4'-isopropylidene-bis- (2,6-dimethylphenol), 4,4'- Butylidene bisphenols such as tylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis- (2,6-di-tert-butylphenol), 4,4'-thiobis- Thiobisphenols such as (3-methyl-6-tert-butylphenol), 4,4′-thiobis- (2,6-di-tert-butylphenol), and phenyl ethers such as bis- (p-hydroxyphenyl) ether Benzophenones such as 4,4′-dihydroxybenzophenone, bisphenyl sulfoxides such as bis- (p-hydroxyphenyl) sulfoxide, and bisphenylsulfones such as bis- (p-hydroxyphenyl) sulfone.
[0017]
Among these, in view of the ability to inhibit polymerization and availability, 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl) The use of (-6-tert-butylphenol) is preferred.
[0018]
In the method of the present invention, a nitroso compound and / or a nitro compound may be added as a polymerization inhibitor separately from the bisphenol compound.
[0019]
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.).
[0020]
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.
[0021]
Among these, considering the ability to inhibit polymerization and the availability, nitroso compounds include N-nitrosophenylhydroxylamine and / or its salts, such as N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum. As the salt or nitro compound, dinitrophenol such as 2,4-dinitrophenol or 2,5-dinitrophenol is preferably used.
[0022]
In the method of the present invention, the addition amount of the polymerization inhibitor is preferably from 1 ppm to 10% by weight, more preferably from 100 ppm to 100% by weight, based on the oxystyrene derivative, taking into consideration its effect and economy. A range of 10,000 ppm is selected, and when adding a nitroso compound or a nitro compound separately from the bisphenol compound, the total amount is preferably 1 ppm to 10% by weight, and more preferably a range of 100 ppm to 10000 ppm.
[0023]
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 suppression and coloring suppression effects 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.
[0024]
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 prevention effect. .
[0025]
【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.
[0026]
Example 1
To a 1000 ml flask, 800 g of PTBS and 4.0 g of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) as a polymerization inhibitor were added. Next, a reflux condenser was attached to the 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 determined. At this time, nitrogen was introduced into the liquid through a capillary. The degree of coloration of the collected PTBS was measured by comparison with a standard APHA solution according to the JIS-K-0071 (1999 edition) test method. The results are shown in Table 1.
[0027]
Examples 2-4
According to Example 1, except that a predetermined amount of the polymerization inhibitor shown in Table 1 was used instead of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) used in Example 1. PTBS was recovered by distillation. The results are shown in Table 1.
[0028]
Example 5
MTBS was recovered by distillation according to Example 1, except that 800 g of MTBS was used instead of PTBS used in Example 1. The results are shown in Table 1.
[0029]
Example 6
In place of PTBS used in Example 1, 800 g of MTBS was used, and in place of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) used, a polymerization inhibitor shown in Table 1 was used for a predetermined amount. Except that, MTBS was recovered by distillation according to Example 1. The results are shown in Table 1.
[0030]
Example 7
PACS was recovered by distillation according to Example 1, except that 800 g of PACS was used instead of PTBS used in Example 1. The results are shown in Table 1.
[0031]
Example 8
In place of PTBS used in Example 1, 800 g of PACS was used, and instead of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) used, a polymerization inhibitor shown in Table 1 was used for a predetermined amount. PACS was recovered by distillation according to Example 1 except that. The results are shown in Table 1.
[0032]
Comparative Examples 1-3
According to Example 1, except that a predetermined amount of the polymerization inhibitor shown in Table 1 was used instead of 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol) used in Example 1. PTBS was recovered by distillation. The results are shown in Table 1.
[0033]
Comparative Example 4
In place of PTBS used in Example 1, 800 g of PACS was used, and instead of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) used, a polymerization inhibitor shown in Table 1 was used for a predetermined amount. PACS was recovered by distillation according to Example 1 except that. The results are shown in Table 1.
[0034]
[Table 1]

【The invention's effect】
As is apparent from the above description, according to the method of the present invention, a high-quality oxystyrene derivative with little color formation and a high quality oxystyrene derivative can be obtained by solving the conventional problems. Distillation is possible with a high recovery rate.

Claims (2)

In distillation of an oxystyrene derivative represented by the following general formula (1) (wherein R represents an alkyl group or an alkylcarbonyl group ), the following general formula (2) (wherein X represents C ₁ -C _{2 alkylene,} .R ₁ and _{R 2} representing a C 2 -C ₅ alkylidene is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, _{R 1} and _{R 2} may be the same or different. Further, m and n represent the number of substituents and are integers of 0 to 4.) A bisphenol-based compound represented by the following formula is added:

2. The oxystyrene derivative according to claim 1, wherein the oxystyrene derivative represented by the general formula (1) is tert-butoxystyrene represented by the following general formula (3) or acetoxystyrene represented by the following general formula (4). Distillation method.