JP3484745B2 - Method for purifying methacrylic acid ester - Google Patents
Method for purifying methacrylic acid esterInfo
- Publication number
- JP3484745B2 JP3484745B2 JP02819194A JP2819194A JP3484745B2 JP 3484745 B2 JP3484745 B2 JP 3484745B2 JP 02819194 A JP02819194 A JP 02819194A JP 2819194 A JP2819194 A JP 2819194A JP 3484745 B2 JP3484745 B2 JP 3484745B2
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- acid ester
- hydroxylamine
- purifying
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、メタクリル酸エステル
に含有される着色物質、特にビアセチル等の不純物を効
率よく且つ経済的に有利に除去することを主眼としたメ
タクリル酸エステルの精製方法に関するものである。メ
タクリル酸エステルは、有機ガラス、光ファイバー、各
種コーティング材、コンタクトレンズ素材等の光学材料
として広く使用されている。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying a methacrylic acid ester, which aims to efficiently and economically remove the coloring substances contained in the methacrylic acid ester, particularly impurities such as biacetyl. Is. Methacrylic acid esters are widely used as optical materials such as organic glass, optical fibers, various coating materials, and contact lens materials.
【０００２】メタクリル酸メチルの工業的な製造法とし
ては、硫安の副生を伴うＡＣＨ法や硫安副生のない改良
ＡＣＨ法、及びＣ4 酸化法等が知られている。また、こ
れらの方法により得られたメタクリル酸やメタクリル酸
メチルをアルコールでエステル化反応やエステル交換反
応を行うことによって種々のメタクリル酸エステルが製
造される。これらの方法によって得られたメタクリル酸
エステルは、その製造の過程において強い酸化剤や高温
に曝されることにより無視することのできない量の着色
原因物質を含有している。メタクリル酸エステルに関し
ては、その用途から着色原因物質の含有の有無はその商
品価値を大きく左右するものである。特に光ファイバー
用途向けなどの場合には、着色原因物質の存在が特定波
長の光の透過率を損なうと云う重要な問題を生ずる。メ
タクリル酸エステルに含有される着色原因物質の除去法
としては、高い段数の塔により高還流比で蒸留分離する
方法、活性炭により吸着処理を行う方法、アルミナ等の
固体吸着剤上を通過させる方法（特公昭60-18964）、芳
香族ジアミン等で処理する方法（EP 206,230）などが知
られている。As an industrial production method of methyl methacrylate, an ACH method accompanied by a by-product of ammonium sulfate, an improved ACH method without an ammonium sulfate by-product, a C 4 oxidation method and the like are known. Further, various methacrylic acid esters are produced by subjecting methacrylic acid or methyl methacrylate obtained by these methods to an esterification reaction or a transesterification reaction with an alcohol. The methacrylic acid ester obtained by these methods contains a strong oxidizing agent or a color-causing substance which cannot be ignored due to exposure to a high temperature during the production process. Regarding the methacrylic acid ester, the commercial value of the methacrylic acid ester largely depends on the use of the methacrylic acid ester. Especially in the case of optical fiber applications, the presence of the color-causing substance causes an important problem that the transmittance of light of a specific wavelength is impaired. As a method for removing the color-causing substance contained in the methacrylic acid ester, a method of distilling and separating at a high reflux ratio by a column with a high number of stages, a method of performing adsorption treatment with activated carbon, a method of passing over a solid adsorbent such as alumina ( Japanese Patent Publication No. Sho 60-18964) and a method of treating with an aromatic diamine (EP 206, 230) are known.
【０００３】[0003]
【発明が解決しようとする課題】これら公知法による着
色原因物質の除去法について種々の検討を試みたが、例
えば、蒸留による方法を適用した場合には、メタクリル
酸メチルの着色原因物質であるビアセチルのように比揮
発度が小さいものを完全に除去するには膨大なエネルギ
ーを必要とすると云う問題があった。また、活性炭を使
用して着色原因物質を充分に除去する場合には、吸脱着
平衡の問題から膨大な量の活性炭が必要となり、また使
用済み活性炭の再生コストが嵩むと云う問題があった。
また、アルミナ上を通過させる方法においても、処理さ
れる着色原因物質に対し膨大な量を要するという欠点が
ある。また、芳香族ジアミンによる方法では、着色原因
物質に対し大過剰の薬剤を必要とし、実用的な方法とは
云えないものであった。Various investigations have been made on the methods for removing the color-causing substance by these known methods. For example, when the method by distillation is applied, biacetyl, which is the color-causing substance of methyl methacrylate, is used. There is a problem that enormous amount of energy is required to completely remove a substance having a small relative volatility such as. Further, when the activated carbon is used to sufficiently remove the coloring-causing substance, a huge amount of activated carbon is required due to the problem of adsorption / desorption equilibrium, and the cost of recycling used activated carbon increases.
In addition, the method of passing over alumina also has a drawback that a huge amount is required for the coloring-causing substance to be treated. Further, the method using an aromatic diamine requires a large excess of a drug for the color-causing substance, and cannot be said to be a practical method.
【０００４】[0004]
【課題を解決するための手段】本発明者は、メタクリル
酸エステルを着色させる原因物質の多くがキノン構造を
持った共役２重結合を有するジケトン及び不飽和ケトン
であることに着目し、これらのカルボニル化合物がヒド
ロキシルアミンと選択的に反応してオキシムを生成し、
一方、ヒドロキシルアミンはメタクリル酸エステルのカ
ルボキシル基とはオキシムを生成しないと云う、この性
質を利用することにより本発明を完成させるに至った。Means for Solving the Problems The present inventor has paid attention to the fact that most of the causative substances for coloring methacrylic acid esters are diketones and unsaturated ketones having conjugated double bonds having a quinone structure. Carbonyl compounds selectively react with hydroxylamine to form oximes,
On the other hand, hydroxylamine does not form an oxime with the carboxyl group of methacrylic acid ester, and the present invention has been completed by utilizing this property.
【０００５】以下に、本発明の方法について詳細に説明
する。本発明は、微量の着色原因物質により着色したメ
タクリル酸エステルの精製法であり、これによりメタク
リル酸エステルを実質的に損失することなく微量の着色
原因物質のみを化学的に物性の大きく異なる物質に変化
せしめ、通常の蒸留操作においても容易に分離可能なも
のとし、実質的に着色物質を含まないメタクリル酸エス
テルを得る方法である。さらに詳しくは、本発明におけ
る着色原因物質が共役２重結合を持つジケトン又は不飽
和ケトンであり、これらをオキシム化またはジオキシム
化することにより高沸点化合物となし、通常の蒸留操作
によって容易に目的のメタクリル酸エステルを得る方法
である。The method of the present invention will be described in detail below. The present invention is a method for purifying a methacrylic acid ester colored with a trace amount of a color-causing substance, whereby only a trace amount of the color-causing substance is chemically converted into a substance having significantly different physical properties without substantially losing the methacrylic acid ester. This is a method of obtaining a methacrylic acid ester that is substantially free of a coloring substance by changing it so that it can be easily separated even in a normal distillation operation. More specifically, the coloring-causing substance in the present invention is a diketone or an unsaturated ketone having a conjugated double bond, which is made into a high-boiling compound by oximation or dioximation, and the objective compound can be easily obtained by ordinary distillation operation. This is a method of obtaining a methacrylic acid ester.
【０００６】本発明において使用するオキシム化剤は、
通常のカルボニル化合物に対するオキシム化剤であれば
何れも使用可能であるが、入手の容易さ、及び取り扱い
の容易さからヒドロキシルアミンの鉱酸塩が好ましく、
特に塩酸ヒドロキシルアミン又は硫酸ヒドロキシルアミ
ンが好適である。ヒドロキシルアミンの鉱酸塩の使用量
は、着色原因物質に含まれるカルボニル基の数に対し、
０．２〜５０倍当量が好ましい。ヒドロキシルアミンの
鉱酸塩の使用量が上記の範囲より少ないと所期の精製効
果が得られず、また上記の範囲より多いと経済的に不利
になるばかりでなく重合等の不都合を生ずる。The oxime-forming agent used in the present invention is
Any oxime-forming agent for a normal carbonyl compound can be used, but a hydroxylamine mineral acid salt is preferable from the viewpoint of easy availability and easy handling,
Hydroxylamine hydrochloride or hydroxylamine sulfate is particularly preferred. The amount of hydroxylamine mineral acid salt used is based on the number of carbonyl groups contained in the color-causing substance.
0.2-50 times equivalent is preferable. If the amount of the hydroxylamine mineral acid salt used is less than the above range, the desired purification effect cannot be obtained, and if it is more than the above range, not only economically disadvantageous but also polymerization and other disadvantages occur.
【０００７】本発明の方法が適用できるメタクリル酸エ
ステルは、如何なる方法によって製造されたものかには
特に限定されない。また本発明の方法は、メタクリル酸
エステルの既存製造プロセスにおいて、最終的な精製メ
タクリル酸エステルを得るための蒸留工程より前の工程
であれば、有効に適用される。The methacrylic acid ester to which the method of the present invention can be applied is not particularly limited by what method is used. Further, the method of the present invention can be effectively applied in the existing manufacturing process of methacrylic acid ester as long as it is a step prior to the distillation step for obtaining the final purified methacrylic acid ester.
【０００８】[0008]
【発明の効果】本発明によれば、着色原因物質を選択的
にオキシム化して分離容易な物質に変化せしめることに
より、極めて着色の少ない高品質のメタクリル酸エステ
ルを容易に得ることが可能となり、工業的に極めて高い
価値を持つ。According to the present invention, it is possible to easily obtain a high quality methacrylic acid ester with very little coloring by selectively oxidizing the coloring causative substance to change it into a substance that is easily separated, It has extremely high industrial value.
【０００９】[0009]
【実施例】以下に、本発明について実施例及び比較例を
以て具体的に詳しく説明するが、本発明はこれらの実施
例によりその範囲を限定されるものではない。実施例１
還流冷却器と撹拌機を備えたフラスコに、０．１重量％
のビアセチルを含有したメタクリル酸メチル５０ｇ及び
メタノ−ル５０ｇを仕込んだ。この液は淡黄色に着色し
ており、色数を表すＡＰＨＡ値は１００であった。次
に、この液に１重量％の塩酸ヒドロキシルアミン水溶液
５．５ｇを加え、室温で２時間撹拌した。この処理液を
ＧＣにより分析したところ、ビアセチルは検出されなか
った。更にこの処理液を水洗してメタノ−ルを除去し、
その有機相を内径１５ｍｍ、高さ３００ｍｍのビグリュ
ウ分留管を備えた蒸留装置で蒸留した。得られたメタク
リル酸メチル留分は無色透明であり、ＡＰＨＡ値は５以
下であった。EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the scope of the present invention is not limited by these examples. Example 1 In a flask equipped with a reflux condenser and a stirrer, 0.1% by weight
50 g of methyl methacrylate containing 50% of biacetyl and 50 g of methanol were charged. This liquid was colored in pale yellow, and the APHA value showing the number of colors was 100. Next, 5.5 g of a 1 wt% hydroxylamine hydrochloride aqueous solution was added to this liquid, and the mixture was stirred at room temperature for 2 hours. When this treated solution was analyzed by GC, biacetyl was not detected. Further, this treatment liquid is washed with water to remove methanol,
The organic phase was distilled using a distillation apparatus equipped with a Vigreux fractionating tube having an inner diameter of 15 mm and a height of 300 mm. The obtained methyl methacrylate fraction was colorless and transparent, and had an APHA value of 5 or less.
【００１０】実施例２
１重量％の塩酸ヒドロキシルアミン水溶液５．５ｇを、
１重量％の硫酸ヒドロキシルアミン水溶液６．５ｇに代
えた以外は、実施例１と同様に行った。その結果、処理
液にビアセチルは検出されず、メタクリル酸メチル留分
のＡＰＨＡ値は５以下であった。 Example 2 5.5 g of a 1% by weight hydroxylamine hydrochloride aqueous solution was added,
Example 1 was repeated except that 6.5 g of a 1 wt% hydroxylamine sulfate aqueous solution was used. As a result, no biacetyl was detected in the treatment liquid, and the APHA value of the methyl methacrylate fraction was 5 or less.
【００１１】実施例３
メタクリル酸メチルをメタクリル酸ブチルに代えた以外
は、実施例１と同様に行った。 その結果、処理液には
ビアセチルは検出されず、メタクリル酸ブチル留分のＡ
ＰＨＡ値は５以下であった。 Example 3 Example 1 was repeated except that methyl methacrylate was replaced with butyl methacrylate. As a result, no biacetyl was detected in the treatment liquid, and the butyl methacrylate fraction A
The PHA value was 5 or less.
【００１２】比較例１
塩酸ヒドロキシルアミン水溶液を加える処理を省いた以
外、実施例１と同様に分析を行った。 その結果、処理
液中にはＧＣにより０．０５重量％のビアセチルが検出
され、メタクリル酸メチル留分のＡＰＨＡ値は７０であ
った。 Comparative Example 1 Analysis was conducted in the same manner as in Example 1 except that the treatment of adding the hydroxylamine hydrochloride aqueous solution was omitted. As a result, 0.05% by weight of biacetyl was detected by GC in the treatment liquid, and the APHA value of the methyl methacrylate fraction was 70.
Claims (3)
されたメタクリル酸エステルを精製するに際し、該カル
ボニル化合物をヒドロキシルアミン又はその塩によりオ
キシム化処理した後に、その処理液を蒸留することによ
りメタクリル酸エステルを分離回収することを特徴とす
るメタクリル酸エステルの精製方法。1. When purifying a methacrylic acid ester colored with a coloring substance having a carbonyl group, the carbonyl compound is subjected to an oximation treatment with hydroxylamine or a salt thereof , and then the treatment liquid is distilled. A method for purifying a methacrylic acid ester, which comprises separating and recovering the methacrylic acid ester.
ム化処理することを特徴とする特許請求の範囲第１項請
求項１記載の方法。2. A Claims first term 請 which comprises treating the oxime by mineral acid salt of hydroxylamine
The method according to claim 1 .
ルである特許請求の範囲第１項請求項１記載の方法。3. The method according to claim 1 , wherein the coloring substance having a carbonyl group is biacetyl.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02819194A JP3484745B2 (en) | 1994-02-25 | 1994-02-25 | Method for purifying methacrylic acid ester |
| US08/381,740 US5587453A (en) | 1994-02-25 | 1995-02-01 | Process for purifying methacrylate |
| DE69505434T DE69505434T2 (en) | 1994-02-25 | 1995-02-08 | Process for cleaning methacrylate |
| DE69523638T DE69523638T2 (en) | 1994-02-25 | 1995-02-08 | Process for cleaning methacrylate |
| EP98104213A EP0855381B1 (en) | 1994-02-25 | 1995-02-08 | Process for purifying methacrylate |
| EP95101612A EP0669313B1 (en) | 1994-02-25 | 1995-02-08 | Process for purifying methacrylate |
| TW084101527A TW326443B (en) | 1994-02-25 | 1995-02-20 | Process for purifying methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02819194A JP3484745B2 (en) | 1994-02-25 | 1994-02-25 | Method for purifying methacrylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07238055A JPH07238055A (en) | 1995-09-12 |
| JP3484745B2 true JP3484745B2 (en) | 2004-01-06 |
Family
ID=12241803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02819194A Expired - Lifetime JP3484745B2 (en) | 1994-02-25 | 1994-02-25 | Method for purifying methacrylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3484745B2 (en) |
-
1994
- 1994-02-25 JP JP02819194A patent/JP3484745B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07238055A (en) | 1995-09-12 |
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