JP4493063B2 - Method for inhibiting polymerization of styrene - Google Patents
Method for inhibiting polymerization of styrene Download PDFInfo
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- JP4493063B2 JP4493063B2 JP2000057179A JP2000057179A JP4493063B2 JP 4493063 B2 JP4493063 B2 JP 4493063B2 JP 2000057179 A JP2000057179 A JP 2000057179A JP 2000057179 A JP2000057179 A JP 2000057179A JP 4493063 B2 JP4493063 B2 JP 4493063B2
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- Prior art keywords
- tetramethyl
- piperidine
- hydroxy
- oxyl
- styrene
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- GXGYVMOSEIGWTR-UHFFFAOYSA-N CC(C)(C)CCCC(C)(C)NO Chemical compound CC(C)(C)CCCC(C)(C)NO GXGYVMOSEIGWTR-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【0001】
【発明の属する技術分野】
スチレンの製造、精製、貯蔵、輸送工程において、該スチレンの重合を抑制することにより工程内での重合物の堆積を抑制し、かつ該スチレンを長期間安定に保持できるようにする方法を提供するものである。
【0002】
【従来の技術】
スチレンは、その製造、精製、貯蔵、輸送工程で熱、過酸化物、金属イオンなどが作用してラジカル重合し易く、蒸留塔、反応塔、リボイラー等の熱交換器、配管等関連装置内に重合物が堆積する。これら重合物が堆積すると熱の伝導が悪くなったり、管内の流れが悪くなるなど操業上大きな支障を来す事になる。
【0003】
従来これらの重合を抑制する為の重合抑制方法として、例えば石油化学のエチレン工程でフェノール類やヒドロキシルアミン類の使用〔米国特許4434307号〕フェニレンジアミン類やニトロソフェノール類の使用〔特開平5−156233号〕、2,2,6,6−テトラメチル−1−オキシル−ピペリジン〔特公平4−26639号〕が、スチレン、アクリル酸、アクリルアミド、ブタジエンなどの各種不飽和単量体の製造工程に対してはニトロフェノール類〔特開昭63−316745号〕、ヒンダードニトロキシル化合物と芳香族ニトロ化合物との組み合わせ〔特開平6−166636号〕などが提案された。最近では2,2,6,6−テトラメチル−4−オキソ−ピペリジン類の優れた重合抑制能に注目され、N−オキシル化合物の使用〔特公昭45−1054号公報〕、4−ヒドロキシ−2,2,6,6−テトラメチル−1−オキシル−ピペリジンまたはこれとハイドロキノンとの併用〔中国特許1052847号〕、2,2,6,6−テトラメチルピペリジン化合物とN−オキシル化合物との併用〔特願平8−48650号〕、N−オキシル化合物、フェノール化合物及びフェノチアジン化合物の併用〔特許2725593号〕、安定なニトロキシラジカル、その対応するヒドロキシルアミンとジヘテロ置換ベンゼン化合物の組み合わせ〔特開平9−124713号〕等が提案されている。
【0004】
【発明が解決しようとする課題】
しかしながら、これまで提案されているN−オキシル化合物とフェノール化合物、フェノチアジン化合物、ピペリジン化合物等の還元性化合物との併用や、N−オキシル化合物とその対応するヒドロキシルアミンとの組み合わせは、重合禁止剤と重合抑制剤の相乗効果を期待したものであり早期の重合抑制にはそれなりの効果がみられるが、装置内での滞留時間等を考慮した場合系内の酸素によって生じる過酸化物ラジカルによる重合反応を制御するには不充分であった。
【0005】
そこで、本発明はスチレンの早期の重合抑制のみならず、装置内での滞留時間を考慮し、系内に発生した過酸化物ラジカルの捕捉にも効果を示し、スチレンの重合を効率的に抑制する方法を提供することにある。
【0006】
【課題を解決する手段】
本発明者らはスチレンの重合反応の特性を詳しく研究した結果、立体障害基を有するN−オキシル化合物と、立体障害基を有するN−ヒドロキシピペリジン化合物、および立体障害基を有するピペリジン化合物を組み合わせることにより、立体障害基を有するN−オキシル化合物のもつ初期の重合抑制効果を維持しつつ、かつ相乗効果が発揮され、長時間に亙って重合抑制効果が持続する事を見出し本発明をなすに至った。
【0007】
すなわち請求項1の発明は、スチレンの製造、精製、貯蔵、あるいは輸送工程において、(A)2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−ヒドロキシ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−オキソ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−メトキシ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−カルボキシ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−カルボキサミド−2,2,6,6−テトラメチル−1−オキシル−ピペリジンよりなる群から選らばれる1種以上と、(B)2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−ヒドロキシ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−オキソ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−メトキシ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−カルボキシ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−カルボキサミド−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジンよりなる群から選らばれる1種以上と、(C)2,2,6,6−テトラメチルピペリジン、4−ヒドロキシ−2,2,6,6−テトラメチルピペリジン、4−オキソ−2,2,6,6−テトラメチルピペリジン、4−メトキシ−2,2,6,6−テトラメチルピペリジン、4−カルボキシ−2,2,6,6−テトラメチルピペリジン、4−カルボキサミド−2,2,6,6−テトラメチルピペリジンよりなる群から選らばれる1種以上とを組み合せてスチレン中に添加することを特徴とするスチレンの重合抑制方法である。
【0008】
【発明の実施の形態】
以下、本発明について詳細に説明する。
【0009】
本発明(A)成分は、2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−ヒドロキシ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−オキソ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−メトキシ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−カルボキシ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン、4−カルボキサミド−2,2,6,6−テトラメチル−1−オキシル−ピペリジンなどであり、これらを2種以上組み合わせてもよい。代表的な2,2,6,6−テトラメチル−1−オキシル−ピペリジンの化学構造を〔化1〕に図示した。
【化1】
【0010】
(B)成分は、2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−ヒドロキシ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−オキソ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−メトキシ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−カルボキシ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン、4−カルボキサミド−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジンであり、これらを2種以上組み合わせてもよい。代表的な2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジンの化学構造を〔化2〕に図示した。
【化2】
【0011】
(C)成分は、2,2,6,6−テトラメチルピペリジン、4−ヒドロキシ−2,2,6,6−テトラメチルピペリジン、4−オキソ−2,2,6,6−テトラメチルピペリジン、4−メトキシ−2,2,6,6−テトラメチルピペリジン、4−カルボキシ−2,2,6,6−テトラメチルピペリジン、4−カルボキサミド−2,2,6,6−テトラメチルピペリジンであり、これらを2種以上組み合わせてもよい。代表的な2,2,6,6−テトラメチルピペリジンの化学構造を〔化3〕に図示した。
【化3】
【0012】
本発明で使用される重合抑制剤の添加量は対象とするスチレンの工程条件、重合抑制の必要度などにより異なり一律に定義できないが、一般的には(A)成分をスチレンに対して10〜10,000ppm、好ましくは100〜5,000ppmであり、(B)成分は、A成分100重量部に対し0.1〜5重量部、好ましくは0.5〜2重量部、(C)成分は、A成分100重量部に対し0.1〜5重量部、好ましくは0.5〜2重量部である。この範囲より少ないと本発明の目的とする相乗効果の発現が小さいことがあり、またこの範囲より多いと効果の発現は充分あるが添加量の割には効果は大きくなく不経済になることがある。
【0013】
本発明の重合抑制方法は(A)(B)(C)各成分を目的とする工程内流体に添加すれば良く、添加方法は特に限定されるものではないが、予め原料に添加するか、蒸留塔、反応塔の塔頂部、塔底部、あるいは貯蔵タンクに添加する。各成分は固体のまま添加してもよいが、目的とする工程内を流れる該スチレンなどを溶剤とした溶液にして添加するのが便利である。また各成分は別々に添加しても、各成分を混合して添加してもよいが、実用上は各成分を所定割合に混合した溶液を作り、これを添加するのがよい。
【0014】
本発明の適用するにあたり、本発明に悪い影響を及ぼさない範囲においてその他の重合抑制剤、分散剤と一緒に添加することがあるが、本発明はそれらの併用を何ら制限するものではない。
【0015】
本発明における(A)成分はN−ニトロキシラジカルであり、主に炭素ラジカルと結合して該ラジカルを不活性にする。(B)成分および(C)成分は主に過酸化物ラジカルを捕捉しスチレンの重合抑制に寄与する。(B)成分は過酸化物ラジカルと反応すると、水素原子を放出し、また(C)成分は過酸化物ラジカルと反応して酸素原子を得てそれぞれ対応する2,2,6,6−テトラメチル−1−オキシル−ピペリジン類に変換し、それらはまた、系内の炭素ラジカル捕捉に使われるので非常に効率的である。(B)成分と(C)成分は過酸化物ラジカルを攻撃するが、その攻撃の仕方が異なることから、両者が共存することにより、より有効に効率よく作用する。
【0016】
【実施例】
実施例によって、本発明をさらに詳細に説明するが、本発明は以下の実施例に限定される物ではない。
【0017】
[試験に用いた化合物]
(1)A成分化合物
A−1:4−ヒドロキシ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン
A−2:4−オキソ−2,2,6,6−テトラメチル−1−オキシル−ピペリジン
(2)B成分化合物
B−1:4−ヒドロキシ−2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン
B−2:2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン
(3)C成分化合物
C−1:4−ヒドロキシ−2,2,6,6−テトラメチルピペリジン
C−2:4−メトキシ−2,2,6,6−テトラメチルピペリジン
【0018】
〔実施例1〕(スチレンの重合抑制)
還流冷却器を備えた4つ口セパラブルフラスコにスチレンモノマー100gを入れ、重合抑制剤を所定量加え、窒素ガスを10分間吹き込んだ。次いでこれを窒素雰囲気下に110℃に保持し、一定時間毎に内容物の一部を取り出し、液中のポリマー生成量を測定した。ポリマー生成量はサンプリングした液の9倍量(容量)のメタノールを加えるとポリマーが液中に懸濁状態に析出してくるのでこれを濾過してポリマー重量を秤量し、モノマー中のポリマー量(%)を求めた。なお、本実験を始める前に、スチレンモノマーをアルカリ洗浄してモノマー中に含まれる重合抑制剤を除き、水洗、乾燥した。
【0019】
得られた結果を表1に示した。
【表1】
【0020】
以上の結果から、本発明の特定の2,2,6,6−テトラメチル−1−オキシル−ピペリジン化合物、特定の2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン化合物、および特定の2,2,6,6−テトラメチルピペリジン化合物を組み合せてスチレンモノマー中に添加することにより、それぞれ単独または2成分の組み合わせよりもスチレンの重合抑制効果が優れている事が分る。特に、特定の2,2,6,6−テトラメチル−1−オキシル−ピペリジン化合物は初期の重合をよく抑制し、これに本発明の組み合わせによって、相乗効果が発揮され、長時間に亙って重合抑制効果が持続する事が了解される。
【0021】
【発明の効果】
スチレンの製造、精製、貯蔵或いは輸送工程において、特定の2,2,6,6−テトラメチル−1−オキシル−ピペリジン化合物、特定の2,2,6,6−テトラメチル−1−ヒドロキシ−ピペリジン化合物、および特定の2,2,6,6−テトラメチルピペリジン化合物を組み合せてスチレンあるいはこれを含有するプロセス流体に加えることにより、該スチレンの重合を効率よく抑制し、且つその効果が長く持続し、関連装置内のファウリング(汚れ)発生量を少なくし、設備の安全運転を容易にする事を可能にした。[0001]
BACKGROUND OF THE INVENTION
Styrene production, purification, storage, in the transport process, to suppress the deposition of polymer in the process by inhibiting the polymerization of the styrene, and provides a method to allow long term stable hold the styrene Is.
[0002]
[Prior art]
Styrene is easily radically polymerized by the action of heat, peroxides, metal ions, etc. during its production, purification, storage, and transportation processes. It is used in heat exchangers such as distillation towers, reaction towers, and reboilers, and in piping and related equipment. A polymer is deposited. When these polymers are deposited, the heat conduction is deteriorated and the flow in the pipe is deteriorated.
[0003]
Conventionally, as a polymerization suppression method for suppressing these polymerizations, for example, use of phenols and hydroxylamines in a petrochemical ethylene process [US Pat. No. 4,434,307] use of phenylenediamines and nitrosophenols [JP-A-5-156233] No.], 2,2,6,6-tetramethyl-1-oxyl-piperidine [Japanese Patent Publication No. 4-26639] is used for the production process of various unsaturated monomers such as styrene, acrylic acid, acrylamide and butadiene. In particular, nitrophenols [Japanese Patent Laid-Open No. 63-316745], combinations of hindered nitroxyl compounds and aromatic nitro compounds [Japanese Patent Laid-Open No. 6-166636] have been proposed. Recently, attention has been paid to the excellent polymerization inhibitory ability of 2,2,6,6-tetramethyl-4-oxo-piperidines, the use of N-oxyl compounds (Japanese Patent Publication No. 45-1054), 4-hydroxy-2 , 2,6,6-tetramethyl-1-oxyl-piperidine or a combination thereof with hydroquinone [Chinese Patent No. 1052847], a combination of a 2,2,6,6-tetramethylpiperidine compound and an N-oxyl compound [ Japanese Patent Application No. 8-48650], N-oxyl compounds, phenol compounds and phenothiazine compounds in combination [Patent No. 2725593], stable nitroxy radicals, combinations of the corresponding hydroxylamines and dihetero-substituted benzene compounds 124713] etc. have been proposed.
[0004]
[Problems to be solved by the invention]
However, the combined use of N-oxyl compounds and reducing compounds such as phenolic compounds, phenothiazine compounds, and piperidine compounds, and the combination of N-oxyl compounds and the corresponding hydroxylamines, are proposed as polymerization inhibitors. The synergistic effect of the polymerization inhibitor is expected, and some effects can be seen in early polymerization suppression, but the polymerization reaction due to peroxide radicals generated by oxygen in the system when considering the residence time in the equipment etc. It was not enough to control.
[0005]
Therefore, the present invention not only suppresses the early polymerization of styrene , but also takes into account the residence time in the equipment, and is effective in trapping peroxide radicals generated in the system, effectively suppressing the polymerization of styrene. It is to provide a way to do.
[0006]
[Means for solving the problems]
As a result of detailed studies on the characteristics of the polymerization reaction of styrene, the present inventors combined an N-oxyl compound having a sterically hindered group, an N-hydroxypiperidine compound having a sterically hindered group, and a piperidine compound having a sterically hindered group. Thus, while maintaining the initial polymerization inhibitory effect of the N-oxyl compound having a sterically hindered group, the synergistic effect is exhibited, and the polymerization inhibitory effect is sustained over a long time. It came.
[0007]
That the invention of claim 1, styrene production, purification, storage, or in the transport step, (A) 2,2,6,6-tetramethyl-1-oxyl - piperidine, 4-hydroxy-2,2,6 , 6-Tetramethyl-1-oxyl-piperidine, 4-oxo-2,2,6,6-tetramethyl-1-oxyl-piperidine, 4-methoxy-2,2,6,6-tetramethyl-1- Selected from the group consisting of oxyl-piperidine, 4-carboxy-2,2,6,6-tetramethyl-1-oxyl-piperidine, 4-carboxamide-2,2,6,6-tetramethyl-1-oxyl-piperidine and one or more of barrel, (B) 2,2,6,6-tetramethyl-1-hydroxy - piperidine, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxy - Pipet Gin, 4-oxo-2,2,6,6-tetramethyl-1-hydroxy-piperidine, 4-methoxy-2,2,6,6-tetramethyl-1-hydroxy-piperidine, 4-carboxy-2, One or more selected from the group consisting of 2,6,6-tetramethyl-1-hydroxy-piperidine, 4-carboxamide-2,2,6,6-tetramethyl-1-hydroxy-piperidine , (C) 2 , 2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2 , 6,6-tetramethylpiperidine, 4-carboxy-2,2,6,6-tetramethylpiperidine, 4-carboxamide-2,2,6,6-tetramethylpiperidine A combination of one or more and the Bareru independent from Ru polymerization inhibiting method der styrene which comprises adding in styrene.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail .
[0009]
The present invention component (A), 2, 2,6,6-tetramethyl-1-oxyl - piperidine, 4-hydroxy-2,2,6,6-tetramethyl-1-oxyl - piperidine, 4-oxo - 2,2,6,6-tetramethyl-1-oxyl-piperidine, 4-methoxy-2,2,6,6-tetramethyl-1-oxyl-piperidine, 4-carboxy-2,2,6,6- Examples thereof include tetramethyl-1-oxyl-piperidine and 4-carboxamide-2,2,6,6-tetramethyl-1-oxyl-piperidine, and two or more of these may be combined. The chemical structure of representative 2,2,6,6-tetramethyl-1-oxyl-piperidine is shown in [Chemical Formula 1].
[Chemical 1]
[0010]
Component (B), 2, 2,6,6-tetramethyl-1-hydroxy - piperidine, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxy - piperidine, 4-oxo-2, 2,6,6-tetramethyl-1-hydroxy-piperidine, 4-methoxy-2,2,6,6-tetramethyl-1-hydroxy-piperidine, 4-carboxy-2,2,6,6-tetramethyl -1-hydroxy-piperidine, 4-carboxamide-2,2,6,6-tetramethyl-1-hydroxy-piperidine, and two or more thereof may be combined. The chemical structure of a typical 2,2,6,6-tetramethyl-1-hydroxy-piperidine is shown in [Chemical Formula 2].
[Chemical formula 2]
[0011]
Component (C), 2, 2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-carboxy-2,2,6,6-tetramethylpiperidine, 4-carboxamide-2,2,6,6-tetramethylpiperidine, Two or more of these may be combined. The chemical structure of a typical 2,2,6,6-tetramethylpiperidine is shown in [Chemical Formula 3].
[Chemical 3]
[0012]
The addition amount of the polymerization inhibitor to be used in the present invention the conditions as engineering styrene of interest can not be defined in different uniformly due Necessity of polymerization inhibitors, typically the component (A) with respect to styrene 10 The component (B) is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight based on 100 parts by weight of the component A, and the component (C). Is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight per 100 parts by weight of component A. May express purpose and that phase to multiply the effect of the present invention is less than this range is small, also effect is uneconomical not great in spite of the well there is added the amount of expression of the effect is more than this range Sometimes.
[0013]
In the polymerization suppression method of the present invention, the components (A), (B), and (C) may be added to the intended in-process fluid, and the addition method is not particularly limited. Add to distillation tower, reaction tower top, tower bottom or storage tank. Each component may be added as a solid, but it is convenient to add it as a solution using the styrene or the like flowing in the target process as a solvent. In addition, each component may be added separately, or each component may be mixed and added. However, in practice, a solution in which each component is mixed in a predetermined ratio is prepared and added.
[0014]
In applying the present invention, it may be added together with other polymerization inhibitors and dispersants as long as they do not adversely affect the present invention, but the present invention does not limit their combined use.
[0015]
The component (A) in the present invention is an N-nitroxy radical, which mainly binds to a carbon radical to inactivate the radical. The component (B) and the component (C) mainly capture peroxide radicals and contribute to suppression of styrene polymerization. When the component (B) reacts with the peroxide radical, a hydrogen atom is released, and the component (C) reacts with the peroxide radical to obtain an oxygen atom and corresponding 2,2,6,6-tetra each. methyl-1-oxyl - converted to piperidines, they are also highly efficient because the used carbon radical trapping in the system. (B) component (C) is attack the peroxide radicals, since the manner of attack are different, by both coexist, works well more effectively efficiently.
[0016]
【Example】
The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
[0017]
[Compounds used in the test]
(1) Component A compound A-1: 4-hydroxy-2,2,6,6-tetramethyl-1-oxyl-piperidine A-2: 4-oxo-2,2,6,6-tetramethyl-1 -Oxyl-piperidine (2) B component compound B-1: 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxy-piperidine B-2: 2,2,6,6-tetramethyl-1 -Hydroxy-piperidine (3) C component compound C-1: 4-hydroxy-2,2,6,6-tetramethylpiperidine C-2: 4-methoxy-2,2,6,6-tetramethylpiperidine ]
[Example 1 ] (Inhibition of polymerization of styrene)
Into a four-necked separable flask equipped with a reflux condenser, 100 g of styrene monomer was added, a predetermined amount of a polymerization inhibitor was added, and nitrogen gas was blown for 10 minutes. Next, this was kept at 110 ° C. in a nitrogen atmosphere, a part of the contents was taken out at regular intervals, and the amount of polymer produced in the liquid was measured. The amount of polymer produced is 9 times the volume of the sampled liquid (volume). When the polymer is precipitated in suspension in the liquid, it is filtered to weigh the polymer weight, and the amount of polymer in the monomer ( %). Before starting this experiment, the styrene monomer was washed with alkali to remove the polymerization inhibitor contained in the monomer, and then washed with water and dried.
[0019]
The obtained results are shown in Table 1 .
[Table 1]
[0020]
From the above results, the specific 2,2,6,6-tetramethyl-1-oxyl-piperidine compound, the specific 2,2,6,6-tetramethyl-1-hydroxy-piperidine compound of the present invention, and the specific It can be seen that by adding these 2,2,6,6-tetramethylpiperidine compounds in combination to the styrene monomer, the effect of inhibiting the polymerization of styrene is superior to that of a single component or a combination of two components. In particular, the specific 2,2,6,6-tetramethyl-1-oxyl-piperidine compound suppresses the initial polymerization well, and the synergistic effect is exhibited by the combination of the present invention, and it can be used for a long time. It is understood that the polymerization inhibitory effect lasts.
[0021]
【The invention's effect】
Specific 2,2,6,6-tetramethyl-1-oxyl-piperidine compound , specific 2,2,6,6-tetramethyl-1-hydroxy-piperidine in styrene production, purification, storage or transportation process compound and by adding a specific 2,2,6,6-tetramethylpiperidine compound in combination styrene or process fluid containing it, polymerization of the styrene was efficiently suppressed, and the effect is long lasting This reduces the amount of fouling (dirt) generated in related equipment and facilitates safe operation of equipment.
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JPH09268138A (en) * | 1996-04-02 | 1997-10-14 | Hakuto Co Ltd | Polymerization suppression of styrene |
JP2001181252A (en) * | 1999-12-24 | 2001-07-03 | Nippon Shokubai Co Ltd | Method of stabilizing n-oxyl compound in vinyl compound |
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JPH09268138A (en) * | 1996-04-02 | 1997-10-14 | Hakuto Co Ltd | Polymerization suppression of styrene |
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