JP2005281208A - Method of suppressing polymerization of (meth)acrylic acid and (meth)acrylate - Google Patents
Method of suppressing polymerization of (meth)acrylic acid and (meth)acrylate Download PDFInfo
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本発明は、（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法に関するものである。更に詳しくは、（メタ）アクリル酸および（メタ）アクリル酸エステルの製造工程、精製工程、貯蔵もしくは輸送工程における重合抑制方法に関する。 The present invention relates to a method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester. More specifically, the present invention relates to a method for inhibiting polymerization in the production process, purification process, storage or transport process of (meth) acrylic acid and (meth) acrylic acid ester.
（メタ）アクリル酸および（メタ）アクリル酸エステルは、極めて重合しやすく、製造工程、精製工程、貯蔵および輸送中、エステル化反応工程時に熱、光、その他の要因により、しばしば重合トラブルを起こすことが知られている。このような重合は（メタ）アクリル酸および（メタ）アクリル酸エステルの製造工程、精製工程での汚れ（ファウリング）の原因となっている。このような汚れが、（メタ）アクリル酸および（メタ）アクリル酸エステルの製造工程、精製工程の製造タンク、蒸留塔（精留塔塔）、液送配管に付着すると、（メタ）アクリル酸および（メタ）アクリル酸エステルの製造・精製が制御できなくなり、操業に支障を来す場合がある。さらに製品品質の低下の原因ともなる。また、（メタ）アクリル酸および（メタ）アクリル酸エステルの汚れ、およびその重合反応物の除去は、人力による作業で行なわざるを得ないために、作業効率が悪く、その結果、長期間の運転停止を引き起こし、経済的損失が大きい。そこで、種々の（メタ）アクリル酸および（メタ）アクリル酸エステルの汚れ抑制剤、汚れ抑制方法や重合抑制剤、重合抑制方法が提案・実施されてきた。 (Meth) acrylic acid and (meth) acrylic acid esters are extremely easy to polymerize, and often cause polymerization problems during the esterification reaction process during the production process, purification process, storage and transport, due to heat, light, and other factors. It has been known. Such polymerization is a cause of fouling in the production process and purification process of (meth) acrylic acid and (meth) acrylic acid ester. When such dirt adheres to the production process of (meth) acrylic acid and (meth) acrylic acid ester, the production tank of the purification process, the distillation tower (rectification tower tower), and the liquid feed pipe, (meth) acrylic acid and Production and purification of (meth) acrylic acid esters can no longer be controlled, which may hinder operations. In addition, it may cause a reduction in product quality. In addition, the removal of dirt of (meth) acrylic acid and (meth) acrylic acid ester and the polymerization reaction product thereof is unavoidable due to human work, resulting in poor work efficiency, resulting in long-term operation. Causes outages and high economic losses. Accordingly, various (meth) acrylic acid and (meth) acrylic acid ester stain inhibitors, stain inhibiting methods, polymerization inhibitors, and polymerization inhibiting methods have been proposed and implemented.
例えば、フェノチアジン化合物とキノン化合物を用いる（メタ）アクリル酸の重合抑制方法（例えば特許文献１および特許文献２参照）、フェニレンジアミン等の芳香族アミン化合物とキノン化合物を用いる（メタ）アクリル酸の重合抑制方法（例えば特許文献３参照）、ハイドロキノン及びその誘導体等のフェノール化合物を用いる（メタ）アクリル酸の重合抑制方法（例えば特許文献４参照）、ピペリジン−１−オキシル化合物と、フェノチアジン、フェノール化合物、芳香族アミン化合物のいずれかとを併用する（メタ）アクリル酸の重合抑制方法（例えば特許文献５参照）、ピペリジン−１−オキシル化合物とフェノール化合物を併用する（メタ）アクリル酸の重合抑制方法（例えば特許文献６参照）が開示されている。 For example, a method for inhibiting polymerization of (meth) acrylic acid using a phenothiazine compound and a quinone compound (see, for example, Patent Document 1 and Patent Document 2), polymerization of (meth) acrylic acid using an aromatic amine compound such as phenylenediamine and a quinone compound Inhibition method (for example, see Patent Document 3), polymerization inhibition method for (meth) acrylic acid using phenol compounds such as hydroquinone and its derivatives (for example, see Patent Document 4), piperidine-1-oxyl compound, phenothiazine, phenol compound, Method for inhibiting polymerization of (meth) acrylic acid in combination with any of aromatic amine compounds (for example, see Patent Document 5), Method for inhibiting polymerization of (meth) acrylic acid in combination with piperidine-1-oxyl compound and phenol compound (for example, Patent Document 6) is disclosed.
しかしながら、これらの方法では、（メタ）アクリル酸および（メタ）アクリル酸エステルの着色の原因となるだけでなく、満足しうるような汚れの原因となる（メタ）アクリル酸および（メタ）アクリル酸エステルの重合の抑制方法は未だ得られず、その改善が強く望まれていた。 However, in these methods, (meth) acrylic acid and (meth) acrylic acid not only cause coloring of (meth) acrylic acid and (meth) acrylic acid ester but also cause satisfactory stains. A method for inhibiting the polymerization of the ester has not yet been obtained, and an improvement has been strongly desired.
本発明は、（メタ）アクリル酸および（メタ）アクリル酸エステルの製造工程、精製工程、貯蔵および輸送工程において、当該工程の汚れの原因にもなっている（メタ）アクリル酸および（メタ）アクリル酸エステルの重合物の抑制方法であり、さらには（メタ）アクリル酸および（メタ）アクリル酸エステルの着色の原因になることがない、（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法を提供することにある。 The present invention provides (meth) acrylic acid and (meth) acrylic acid, which are also causes of contamination in the production process, purification process, storage and transport process of (meth) acrylic acid and (meth) acrylic acid ester. Inhibiting polymerization of acid ester polymer, and further inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester, which does not cause coloring of (meth) acrylic acid and (meth) acrylic acid ester It is to provide a method.
本発明者らは、前記の問題点を克服すべく、（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制について鋭意検討した結果、特定のポリエチレンイミン化合物と従来の重合抑制剤を同時に用いることにより、（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制効果を飛躍的に向上させることを見出し、本発明を完成するに至った。 In order to overcome the above-described problems, the present inventors have conducted extensive studies on the polymerization inhibition of (meth) acrylic acid and (meth) acrylic acid ester. As a result, a specific polyethyleneimine compound and a conventional polymerization inhibitor are simultaneously used. As a result, it has been found that the polymerization inhibition effect of (meth) acrylic acid and (meth) acrylic acid ester is drastically improved, and the present invention has been completed.
即ち、請求項１に係る発明は、（メタ）アクリル酸および（メタ）アクリル酸エステルの製造工程、精製工程、貯蔵および輸送工程における重合抑制方法であって、（Ａ）ポリエチレンイミン（分子量３００〜５００，０００）および／又はその付加変性物と、（Ｂ）一般式（１）（式中、Ｘは、水素原子、酸素原子、水酸基、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のカルボン酸または炭素数１〜３のアミド基を示す。）で表されるピペリジン−１−オキシル化合物、一般式（２）（式中、Ｒ１、Ｒ２は独立して水素原子、水酸基、炭素数１〜３のアルコキシ基、炭素数４〜１８のアルキル基、アリール基、ベンジル基、α−ベンジル基を示す。）で表されるフェノチアジン化合物、一般式（３）（式中、Ｒ３は水素原子、炭素数４〜１８のアルキル基、炭素数６〜１４のアリール基を示し、Ｒ４は炭素数１〜１８のアルキルアミノ基、炭素数６〜１４のアリールアミノ基を示す。）で表される芳香族アミン化合物、一般式（４）（式中、Ｒ５は水素、炭素数１〜３のアルキル基を示す。）で表されるフェノール化合物の１種以上を該工程に同時に用いることを特徴とする（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法である。 That is, the invention according to claim 1 is a polymerization suppression method in the production process, purification process, storage and transport process of (meth) acrylic acid and (meth) acrylic acid ester, and comprises (A) polyethyleneimine (molecular weight 300 to 300). 500,000) and / or addition-modified products thereof, and (B) general formula (1) (wherein X is a hydrogen atom, an oxygen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms). A piperidine-1-oxyl compound represented by general formula (2) (wherein R 1 and R 2 are represented by the following formula: alkoxy group, carboxylic acid having 1 to 3 carbon atoms or amide group having 1 to 3 carbon atoms). Independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 4 to 18 carbon atoms, an aryl group, a benzyl group, or an α-benzyl group), a general formula (3) (in the formula R 3 is a hydrogen atom, an alkyl group having 4 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, R 4 represents an alkylamino group, an arylamino group having 6 to 14 carbon atoms having 1 to 18 carbon atoms And at least one phenol compound represented by the general formula (4) (wherein R 5 represents hydrogen or an alkyl group having 1 to 3 carbon atoms). And (meth) acrylic acid and (meth) acrylic acid ester polymerization inhibiting method.
請求項３に係る発明は、請求項１又は２記載の（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法であり、（Ｂ）成分が、フェノチアジン、ｐ−フェニレンジアミン、ジフェニルアミン、ハイドロキノン、ハイドロキノンモノメチルエーテル（メトキノン）、２，２，６，６−テトラメチルピペリジン−１−オキシル、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４−オキソ−２，２，６，６−テトラメチルピペリジン−１−オキシルの１種以上であることを特徴としている。 The invention according to claim 3 is the method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester according to claim 1 or 2, wherein component (B) is phenothiazine, p-phenylenediamine, diphenylamine, hydroquinone. , Hydroquinone monomethyl ether (methoquinone), 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2, It is characterized by being at least one of 2,6,6-tetramethylpiperidine-1-oxyl.
請求項４に係る発明は、請求項１乃至３のいずれか記載の（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法であり、（Ａ）成分と（Ｂ）成分を５：９５〜８０：２０の比率で用いることを特徴としている。 The invention according to claim 4 is the method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester according to any one of claims 1 to 3, wherein (A) component and (B) component are mixed with 5:95. It is characterized by being used at a ratio of ˜80: 20.
本発明の（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法は、従来から使用されて来た重合抑制剤とポリエチレンイミンと併用することにより、（メタ）アクリル酸および（メタ）アクリル酸エステルの着色の原因になることなく、しかも（メタ）アクリル酸および（メタ）アクリル酸エステルの製造工程、精製工程、貯蔵もしくは輸送時の（メタ）アクリル酸および（メタ）アクリル酸エステルの汚れの抑制と重合を抑制することができ、そのコスト削減をもたらすだけでなく、製造装置等への汚れ付着や重合による操業の停止等によって生じる大きな経済的損失の改善に大きく寄与する。 The method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester according to the present invention can be achieved by using (meth) acrylic acid and (meth) acrylic in combination with a conventional polymerization inhibitor and polyethyleneimine. Stain of (meth) acrylic acid and (meth) acrylic acid ester during production, purification, storage or transportation of (meth) acrylic acid and (meth) acrylic acid ester without causing acid ester coloring In addition to not only reducing the cost but also reducing the cost, it greatly contributes to the improvement of a large economic loss caused by the adhesion of dirt to the manufacturing apparatus or the like, or the stoppage of the operation due to the polymerization.
本発明は、（メタ）アクリル酸および（メタ）アクリル酸エステルの製造、精製、貯蔵および輸送工程における（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制および重合によって生じる汚れの発生抑制・防止を効果的に達成し得る重合抑制方法であり、（Ａ）特定のポリエチレンイミン化合物（以下、「（Ａ）成分」とする）と、（Ｂ）フェノチアジン化合物、芳香族アミン化合物、フェノール化合物、ピペリジン−Ｎ−オキシル化合物の１種以上（以下、「（Ｂ）成分」とする）を同時に当該工程に用いることを特徴とする（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法である。更に詳しくは、（Ａ）成分に（Ｂ）成分を加えることにより、（Ｂ）成分の重合抑制効果を予想し得ないほど、著しく向上させた（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法および汚れの抑制方法である。 In the present invention, (meth) acrylic acid and (meth) acrylic acid ester production, purification, storage and transportation process (meth) acrylic acid and (meth) acrylic acid ester polymerization inhibition and generation of dirt caused by polymerization A polymerization inhibiting method capable of effectively achieving prevention, (A) a specific polyethyleneimine compound (hereinafter referred to as “component (A)”), (B) a phenothiazine compound, an aromatic amine compound, a phenol compound, One or more of piperidine-N-oxyl compounds (hereinafter referred to as “component (B)”) are simultaneously used in the step, and the method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester is used. is there. More specifically, by adding the (B) component to the (A) component, the (meth) acrylic acid and the (meth) acrylic acid ester that have been remarkably improved so that the polymerization inhibiting effect of the (B) component cannot be expected. It is a polymerization inhibiting method and a soil inhibiting method.
本発明における（メタ）アクリル酸は、アクリル酸またはメタクリル酸であり、その製造方法は特に限定されるものでは無く、プロピレンあるいはイソブチレンから（メタ）アクロレインを経由して生成させる接触気相酸化法、アセトンを原料としてアセトンシアンヒドリン（ＡＣＨ）を経由してメタクリル酸を得るＡＣＨ法等が挙げられる。 (Meth) acrylic acid in the present invention is acrylic acid or methacrylic acid, and the production method thereof is not particularly limited, and a catalytic gas phase oxidation method in which propylene or isobutylene is produced via (meth) acrolein, Examples thereof include an ACH method in which methacrylic acid is obtained from acetone as a raw material via acetone cyanohydrin (ACH).
本発明における（メタ）アクリル酸エステルは、具体的にはアクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル、アクリル酸２−ヒドロキシエチル、アクリル酸２−ヒドロキシプロピル、メタクリル酸メチル、メタクリル酸ブチル、メタクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシプロピル等が挙げられる。また、（メタ）アクリル酸とアルキレンオキシド（例えば、エチレンオキサイド）、高級脂肪酸（例えば、ステアリルアルコール）、有機金属（例えば、トリブチル錫オキサイド）等との反応にも適用することができ、その際に触媒として硫酸、ｐ−トルエンスルホン酸、陽イオン交換樹脂等を使用しても良い。 Specifically, the (meth) acrylic acid ester in the present invention is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate. , Butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and the like. It can also be applied to the reaction of (meth) acrylic acid with alkylene oxide (for example, ethylene oxide), higher fatty acid (for example, stearyl alcohol), organic metal (for example, tributyltin oxide), etc. As the catalyst, sulfuric acid, p-toluenesulfonic acid, cation exchange resin or the like may be used.
本発明における（メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制および汚れの発生の抑制・防止の対象となる工程は、製造工程での反応タンク、貯蔵タンク、蒸留塔、熱交換器、液送配管およびその付随周辺設備等があげられ、精製工程では精留塔、貯留タンク、未反応の（メタ）アクリル酸および（メタ）アクリル酸エステルの回収装置およびその回収貯留タンク、熱交換器、液送配管およびその付随周辺設備等、貯蔵および輸送工程では貯蔵タンクや貯蔵コンテナ、輸送コンテナ、移送配管およびその付随周辺設備等があげられる。 In the present invention, (meth) acrylic acid and (meth) acrylic acid ester polymerization inhibition and the process to be subject to suppression / prevention of stains are the reaction tank, storage tank, distillation tower, heat exchanger in the production process, Examples include liquid feed pipes and associated peripheral equipment. In the purification process, rectification towers, storage tanks, unreacted (meth) acrylic acid and (meth) acrylic acid ester recovery devices, and their recovery storage tanks, heat exchangers In the storage and transportation processes, liquid tanks and storage containers, transport containers, transfer pipes and their associated peripheral equipment, etc. are included.
本発明で用いる（Ａ）成分は、ポリエチレンイミンおよびポリエチレンイミン付加変性物（以下、「ポリエチレンイミン化合物」とする。）である。 The component (A) used in the present invention is polyethyleneimine and a polyethyleneimine addition-modified product (hereinafter referred to as “polyethyleneimine compound”).
ポリエチレンイミンは、エチレンイミンの重合体であり、その平均重量分子量は３００〜５００，０００であり、好ましくは１，０００〜２００，０００、より好ましくは１０，０００〜７０，０００である。ポリエチレンイミンの平均重量分子量が３００未満では本発明の効果が十分に発揮されないことがある。また、５００，０００を超える平均重量分子量のものは、平均重量分子量の増加に伴う、重合抑制効果の向上が大きくなく、また入手が容易ではない場合があり、好ましくない。本発明で用いるポリエチレンイミンは、特に限定されるものではなく、通常、エチレンイミンを触媒の存在下、開環重合させて得られる。具体的には、日本触媒（株）により製造販売されている「エポミン」シリーズがある。 Polyethyleneimine is a polymer of ethyleneimine and has an average weight molecular weight of 300 to 500,000, preferably 1,000 to 200,000, more preferably 10,000 to 70,000. When the average weight molecular weight of polyethyleneimine is less than 300, the effects of the present invention may not be sufficiently exhibited. Moreover, the thing of the average weight molecular weight exceeding 500,000 is not preferable because the improvement of a polymerization inhibitory effect accompanying the increase in an average weight molecular weight is not large, and acquisition may not be easy. The polyethyleneimine used in the present invention is not particularly limited and is usually obtained by ring-opening polymerization of ethyleneimine in the presence of a catalyst. Specifically, there is the “Epomin” series manufactured and sold by Nippon Shokubai Co., Ltd.
ポリエチレンイミン付加変性物は、ポリエチレンイミンにエチレンオキシド、プロピレンオキシドあるいはブチレンオキシドの１種以上を付加した変性物、ポリエチレンイミンにアクリロニトリルを付加した変性物、ポリエチレンイミンにビニルメチルエーテルを付加させた変性物である。ポリエチレンイミンへの付加物の割合は、ポリエチレンイミン変性物の目的とする性能を考慮して適宜選択、決定すれば良く、通常、ポリエチレンイミンに対して１〜６０重量％であり、好ましくは５〜４０重量％である。具体的なポリエチレンイミン変性物としては、日本触媒（株）により製造販売されている「エポミンＫＴシリーズ」、「エポミンＰＫシリーズ」がある。 The polyethylenimine addition modified product is a modified product obtained by adding one or more of ethylene oxide, propylene oxide or butylene oxide to polyethylene imine, a modified product obtained by adding acrylonitrile to polyethylene imine, or a modified product obtained by adding vinyl methyl ether to polyethylene imine. is there. The ratio of the adduct to polyethyleneimine may be appropriately selected and determined in consideration of the intended performance of the polyethyleneimine modified product, and is usually 1 to 60% by weight with respect to polyethyleneimine, preferably 5 to 5%. 40% by weight. Specific modified polyethyleneimine includes “Epomin KT series” and “Epomin PK series” manufactured and sold by Nippon Shokubai Co., Ltd.
本発明の（Ａ）成分には、上記のポリエチレンイミンおよびポリエチレンイミン付加変性物の中の１種あるいは２種以上を組合せて用いることができる。 In the component (A) of the present invention, one or a combination of two or more of the above-mentioned polyethyleneimine and polyethyleneimine addition-modified products can be used.
本発明で用いる（Ｂ）成分は、ピペリジン−１−オキシル化合物、フェノチアジン化合物、芳香族アミン化合物、フェノール化合物からなる群より選ばれた１種以上からなる。 (B) component used by this invention consists of 1 or more types chosen from the group which consists of a piperidine-1-oxyl compound, a phenothiazine compound, an aromatic amine compound, and a phenol compound.
ピペリジン−Ｎ−オキシル化合物は、一般式（１）で表され、式中、Ｘは水素原子、酸素原子、水酸基、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のカルボン酸または炭素数１〜３のアミド基を示す。具体的には、２，２，６，６−テトラメチルピペリジン−１−オキシル、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４−オキソ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４，４‘，４“−トリス−（１−オキシル−２，２，６，６−テトラメチルピペリジノ）フォスファイト等があげられる。 The piperidine-N-oxyl compound is represented by the general formula (1), where X is a hydrogen atom, an oxygen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number. A carboxylic acid having 1 to 3 carbon atoms or an amide group having 1 to 3 carbon atoms is shown. Specifically, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6 , 6-tetramethylpiperidine-1-oxyl, 4,4 ', 4 "-tris- (1-oxyl-2,2,6,6-tetramethylpiperidino) phosphite and the like.
ファノチアジン化合物は、一般式（２）で表され、式中、Ｒ１、Ｒ２は独立して水素原子、水酸基、炭素数１〜３のアルコキシ基、炭素数４〜１８のアルキル基、アリール基、ベンジル基、α−ベンジル基を示す。具体的にはフェノチアジン、ビス−（α−メチルベンジル）フェノチアジン、３，７−ジオクチルフェノチアジン、ビス−（α−ジメチルベンジル）フェノチアジン等があげられる。 The fanothiazine compound is represented by the general formula (2), in which R 1 and R 2 are independently a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 4 to 18 carbon atoms, and an aryl group. , A benzyl group and an α-benzyl group. Specific examples include phenothiazine, bis- (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, bis- (α-dimethylbenzyl) phenothiazine and the like.
芳香族アミン化合物は、一般式（３）で表され、式中、Ｒ３は水素原子、炭素数４〜１８のアルキル基、炭素数６〜１４のアリール基を示し、Ｒ４は炭素数１〜１８のアルキルアミノ基、炭素数６〜１４のアリールアミノ基を示す。具体的にはｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、ジフェニルアミン、Ｎ，Ｎ‘−フェニルイソプロピルフェニレンジアミン、Ｎ，Ｎ’−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン等があげられる。 The aromatic amine compound is represented by the general formula (3), in which R 3 represents a hydrogen atom, an alkyl group having 4 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and R 4 represents 1 carbon atom. An alkylamino group having 18 to 18 carbon atoms and an arylamino group having 6 to 14 carbon atoms; Specific examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diphenylamine, N, N′-phenylisopropylphenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, and the like. .
フェノール化合物は、一般式（４）で表され、式中、Ｒ５は水素、炭素数１〜３のアルキル基を示す。具体的にはハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、レゾルシノール等があげられる。これらの内、好ましくはフェノチアジン、ｐ−フェニレンジアミン、ジフェニルアミン、ハイドロキノン、ハイドロキノンモノメチルエーテル（メトキノン）、２，２，６，６−テトラメチルピペリジン−１−オキシル、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４−オキソ−２，２，６，６−テトラメチルピペリジン−１−オキシルであり、その１種以上が用いられる。 The phenol compound is represented by the general formula (4), in which R 5 represents hydrogen or an alkyl group having 1 to 3 carbon atoms. Specific examples include hydroquinone, hydroquinone monomethyl ether, catechol, resorcinol and the like. Of these, phenothiazine, p-phenylenediamine, diphenylamine, hydroquinone, hydroquinone monomethyl ether (methoquinone), 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6, 6-tetramethylpiperidine-1-oxyl and 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, one or more of which are used.
本発明の重合抑制方法は、対象となる工程および箇所に（Ａ）成分と（Ｂ）成分が同時に存在することにより、重合抑制効果に対して予想し得ないような相乗効果が得られるものである。（Ａ）成分と（Ｂ）成分の使用比率は、通常、（Ａ）成分と（Ｂ）成分の重量比で５：９５〜８０：２０、好ましくは２０：８０〜６０：４０、より好ましくは３０：７０〜５０：５０、である。 The polymerization inhibiting method of the present invention is such that a synergistic effect that cannot be expected for the polymerization inhibiting effect can be obtained by the simultaneous presence of the component (A) and the component (B) in the target process and location. is there. The use ratio of the component (A) to the component (B) is usually 5:95 to 80:20, preferably 20:80 to 60:40, more preferably the weight ratio of the component (A) to the component (B). 30: 70-50: 50.
また、（Ａ）成分と（Ｂ）成分の使用量は、プロセスの状況、要求される汚れの抑制、重合抑制の程度に応じて、適宜決定されるものであり、一律に決めることはできないが、通常、（メタ）アクリル酸あるいは（メタ）アクリル酸エステルに対して、（Ａ）成分と（Ｂ）成分のそれぞれの添加量は、０．５〜３００ｐｐｍ、好ましくは１ｐｐｍ〜１００ｐｐｍである。また、（Ａ）成分と（Ｂ）成分の合計添加量は、通常、１〜５００ｐｐｍ、好ましくは２ｐｐｍ〜２００ｐｐｍである。（Ａ）成分と（Ｂ）成分のそれぞれの添加量が、０．５ｐｐｍより少ないと重合抑制効果が十分ではない場合があり、３００ｐｐｍより多すぎても添加量に見合うだけの重合抑制効果が得られず、経済的に不利になる場合がある。 In addition, the amount of the component (A) and the component (B) used is appropriately determined according to the process status, the required level of soil suppression, and the degree of polymerization suppression, and cannot be determined uniformly. Usually, the addition amount of each of the component (A) and the component (B) is 0.5 to 300 ppm, preferably 1 ppm to 100 ppm with respect to (meth) acrylic acid or (meth) acrylic acid ester. Moreover, the total addition amount of (A) component and (B) component is 1-500 ppm normally, Preferably it is 2 ppm-200 ppm. If the addition amount of each of the component (A) and the component (B) is less than 0.5 ppm, the polymerization inhibitory effect may not be sufficient, and if it is more than 300 ppm, a polymerization inhibitory effect sufficient for the addition amount is obtained. May be economically disadvantageous.
本発明の重合抑制方法における（Ａ）成分、（Ｂ）成分の添加場所は、特に限定されるものではないが、通常、（メタ）アクリル酸あるいは（メタ）アクリル酸エステルによる汚れおよび重合体が生成し問題となる工程や箇所、あるいはその上流の工程や箇所に添加される。また、（メタ）アクリル酸エステルの製造では、（メタ）アクリル酸エステルの合成反応工程、（メタ）アクリル酸エステルの精製工程における未反応の原料（メタ）アクリル酸と蒸留分離工程における重合抑制用途として、汚れおよび重合体が生成し問題となる工程や箇所、あるいはその上流の工程や箇所に添加される。 The location of addition of component (A) and component (B) in the polymerization inhibition method of the present invention is not particularly limited, but usually stains and polymers due to (meth) acrylic acid or (meth) acrylic acid esters are present. It is added to a process or location that is a problem to be generated or upstream. Also, in the production of (meth) acrylic acid esters, unreacted raw material (meth) acrylic acid in the (meth) acrylic acid ester synthesis reaction step, (meth) acrylic acid ester purification step, and polymerization suppression use in the distillation separation step As described above, it is added to a process or a part where dirt and a polymer are generated and becomes a problem, or an upstream process or part.
本発明の重合抑制方法における（Ａ）成分、（Ｂ）成分の添加方法は、特に限定されるものではないが、（Ａ）成分および（Ａ）成分をそれぞれ別々に添加する方法、（Ａ）成分および（Ａ）成分をそれぞれ別々に（メタ）アクリル酸あるいは（メタ）アクリル酸エステルに可溶な液体、例えば水に溶解して添加する方法等があり、いずれを用いても良い。また、（Ａ）成分、（Ｂ）成分の添加の順序は、特に限定されるものではなく、任意に決定して良い。 The method for adding the component (A) and the component (B) in the polymerization inhibiting method of the present invention is not particularly limited, but the method for separately adding the component (A) and the component (A), (A) There is a method in which the component and the component (A) are added separately by dissolving in (meth) acrylic acid or (meth) acrylic acid ester, for example, water, and any of them may be used. Moreover, the order of addition of the component (A) and the component (B) is not particularly limited, and may be arbitrarily determined.
また、本発明の重合抑制方法が使用される雰囲気は、窒素等の不活性ガス下でも有効であるが、（メタ）アクリル酸および（メタ）アクリル酸エステルの精製時や反応使用時においては、酸素の存在下で使用する方法も有効である。この場合の酸素の供給方法としては、空気バブリング方式が最も経済的である。 In addition, the atmosphere in which the polymerization suppression method of the present invention is used is effective even under an inert gas such as nitrogen, but at the time of purification of (meth) acrylic acid and (meth) acrylic acid ester or during reaction use, A method for use in the presence of oxygen is also effective. In this case, the air bubbling method is the most economical as the oxygen supply method.
次に実施例により具体的に説明するが、本発明はこれらによって限定されるものではない。 EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
（ポリエチレンイミン化合物）
ＰＥＩ−１：ポリエチレンイミン（平均分子量約６００）（試薬、和光純薬株式会社製）
ＰＥＩ−２：ポリエチレンイミン（平均分子量１８００）（試薬、和光純薬株式会社製）
ＰＥＩ−３：ポリエチレンイミン（平均分子量１０，０００）（試薬、和光純薬株式会社製）
ＰＥＩ−４：ポリエチレンイミン（平均分子量７０，０００）（試薬、和光純薬株式会社製）
ＰＥＩ−５：変性ポリエチレンイミン「エポミンＫＴ−８１７」（試薬、日本触媒株式会社製）
(Polyethyleneimine compound)
PEI-1: Polyethyleneimine (average molecular weight of about 600) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
PEI-2: Polyethyleneimine (average molecular weight 1800) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
PEI-3: Polyethyleneimine (average molecular weight 10,000) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
PEI-4: Polyethyleneimine (average molecular weight 70,000) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
PEI-5: Modified polyethyleneimine “Epomin KT-817” (reagent, manufactured by Nippon Shokubai Co., Ltd.)
（重合抑制剤）
ＰＴＺ：フェノチアジン（試薬、東京化成工業株式会社製）
ＰＤＡ：ｐ−フェニレンジアミン（試薬、東京化成工業株式会社製）
ＨＱ：ハイドロキノン（試薬、東京化成工業株式会社製）
ＭＱ：ハイドロキノンモノメチルエーテル（メトキノン）（試薬、東京化成工業株式会社製）
Ｈ−ＴＥＭＰＯ：４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−1−オキシル（試薬、東京化成工業株式会社製）
(Polymerization inhibitor)
PTZ: Phenothiazine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
PDA: p-phenylenediamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
HQ: Hydroquinone (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
MQ: Hydroquinone monomethyl ether (methoquinone) (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
（重合抑制試験）
アクリル酸中に含まれている重合抑制剤であるハイドロキノンモノメチルエーテル（メトキノン）をアクリル酸の減圧蒸留により除去した後、アクリル酸に所定量の（Ａ）ポリエチレンイミンと（Ｂ）重合抑制剤である４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−1−オキシル（Ｈ−ＴＥＭＰＯ）を添加し、試験液とした。該試験液１０ｇを５０ｍＬ試験管に採り、該試験液に毎分２０ｍｌの窒素を吹き込み、系内の酸素を除去した。窒素の吹き込みを続けながら、試験管を１００℃の油浴中に浸した。重合の開始に伴って、当該試験液中に濁りが発生するまでの時間を誘導期（ＩＰ−ＡＡ）として測定した。誘導期（ＩＰ−ＡＡ）が長いほど、重合抑制効果が高く、好ましい。同様にして各種（Ａ）ポリエチレンイミンと（Ｂ）従来の重合抑制剤を用いて、重合抑制試験を行なった。その結果を表１に示した。
(Polymerization inhibition test)
Hydroquinone monomethyl ether (methoquinone), which is a polymerization inhibitor contained in acrylic acid, is removed by distillation under reduced pressure of acrylic acid, and then a predetermined amount of (A) polyethyleneimine and (B) polymerization inhibitor are added to acrylic acid. 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (H-TEMPO) was added to prepare a test solution. 10 g of the test solution was put into a 50 mL test tube, and 20 ml of nitrogen was blown into the test solution per minute to remove oxygen in the system. The test tube was immersed in an oil bath at 100 ° C. while continuing to blow nitrogen. With the start of the polymerization, the time until turbidity occurred in the test solution was measured as the induction period (IP-AA). The longer the induction period (IP-AA), the higher the polymerization inhibition effect, which is preferable. Similarly, a polymerization inhibition test was conducted using various types of (A) polyethyleneimine and (B) a conventional polymerization inhibitor. The results are shown in Table 1.
同様にアクリル酸に代えて、メタクリル酸を用いた重合抑制試験を行なった。メタクリル酸の場合には試験管の加熱時間を１１０℃とし、誘導期をＩＰ−ＭＡと表示し、その結果を表２に示した。 Similarly, a polymerization inhibition test using methacrylic acid instead of acrylic acid was conducted. In the case of methacrylic acid, the heating time of the test tube was 110 ° C., the induction period was expressed as IP-MA, and the results are shown in Table 2.
従来の重合抑制剤に対して、ポリエチレンイミンを併用することにより、アクリル酸、メタクリル酸の重合抑制効果は予想以上の効果を発揮している。例えば、アクリル酸の場合、表１記載の実施例Ｎｏ．１０のポリエチレンイミンの１ｐｐｍと従来の重合抑制剤：Ｈ−ＴＥＭＰＯの１９ｐｐｍの誘導期間は１５分であり、表１記載の比較例Ｎｏ．１１のＨ−ＴＥＭＰＯ：２０ｐｐｍの誘導期間の８分を大きく上回る重合抑制効果を発揮し、さらにメタクリル酸の場合も同様に表２記載の実施例Ｎｏ．１０のポリエチレンイミンの１ｐｐｍと従来の重合抑制剤：Ｈ−ＴＥＭＰＯの１９ｐｐｍの誘導期間は２０分、表２記載の比較例Ｎｏ．１１のＨ−ＴＥＭＰＯ：２０ｐｐｍの誘導期間の９分と、本発明の方法により重合抑制効果が大きく向上することが分かる。
By using polyethyleneimine in combination with a conventional polymerization inhibitor, the polymerization inhibition effect of acrylic acid and methacrylic acid is more than expected. For example, in the case of acrylic acid, Example No. The induction period of 1 ppm of polyethyleneimine of 10 and 19 ppm of conventional polymerization inhibitor: H-TEMPO is 15 minutes. 11 H-TEMPO: exerts a polymerization inhibitory effect far exceeding 8 minutes of the induction period of 20 ppm, and also in the case of methacrylic acid, Example No. The induction period of 1 ppm of polyethyleneimine of 10 and 19 ppm of conventional polymerization inhibitor: H-TEMPO was 20 minutes. 11 H-TEMPO: 9 minutes of the induction period of 20 ppm, and it can be seen that the polymerization inhibition effect is greatly improved by the method of the present invention.
Claims (4)
The method for inhibiting polymerization of (meth) acrylic acid and (meth) acrylic acid ester according to any one of claims 1 to 3, wherein (A) and (B) are used in a ratio of 5:95 to 80:20.
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| JP2007291041A (en) * | 2006-04-27 | 2007-11-08 | Osaka Organic Chem Ind Ltd | Method for producing adamantyl (meth)acrylate compound |
| JP2014210777A (en) * | 2007-03-23 | 2014-11-13 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for storing monomer phase which is liquid under condition of storage |
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| JPS50106917A (en) * | 1974-01-25 | 1975-08-22 | ||
| JPH11269128A (en) * | 1998-03-19 | 1999-10-05 | Mitsubishi Gas Chem Co Inc | Packing in distillation column for preventing vinyl compound from polymerizing and prevention of polymerization of vinyl compound |
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| JPS50106917A (en) * | 1974-01-25 | 1975-08-22 | ||
| JPH11269128A (en) * | 1998-03-19 | 1999-10-05 | Mitsubishi Gas Chem Co Inc | Packing in distillation column for preventing vinyl compound from polymerizing and prevention of polymerization of vinyl compound |
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| JP2007291041A (en) * | 2006-04-27 | 2007-11-08 | Osaka Organic Chem Ind Ltd | Method for producing adamantyl (meth)acrylate compound |
| JP2014210777A (en) * | 2007-03-23 | 2014-11-13 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for storing monomer phase which is liquid under condition of storage |
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