JPH05320217A - Method for preventing polymerization of (meth) acrylic acid - Google Patents
Method for preventing polymerization of (meth) acrylic acidInfo
- Publication number
- JPH05320217A JPH05320217A JP15451992A JP15451992A JPH05320217A JP H05320217 A JPH05320217 A JP H05320217A JP 15451992 A JP15451992 A JP 15451992A JP 15451992 A JP15451992 A JP 15451992A JP H05320217 A JPH05320217 A JP H05320217A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- meth
- oxyl
- polymerization inhibitor
- polymerization
- 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.)
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- Polymerisation Methods In General (AREA)
Abstract
(57)【要約】
【構成】 （メタ）アクリル酸の精製時、貯蔵もしくは
輸送時またはエステル化反応時に、重合防止剤として、
特定のＮ−オキシル化合物とフェノチアジン、芳香族ア
ミン類、フェノール類化合物とを共存させる。
【効果】 複合型重合抑制剤を共存させる事により、
（メタ）アクリル酸の精製時、貯蔵もしくは輸送時およ
びエステル化反応時に問題となる重合物発生を防止する
事ができる。さらに重合防止剤の添加量を削減すること
が可能となり、着色のより少ない高品質の製品を得る事
ができる。(57) [Summary] [Structure] As a polymerization inhibitor during purification, storage or transportation of (meth) acrylic acid, or esterification reaction,
A specific N-oxyl compound and phenothiazine, aromatic amines, and phenol compounds are allowed to coexist. [Effect] By coexisting with the composite type polymerization inhibitor,
It is possible to prevent generation of a polymer, which is a problem during the purification, storage or transportation of (meth) acrylic acid, and during the esterification reaction. Furthermore, it is possible to reduce the amount of the polymerization inhibitor added, and it is possible to obtain a high-quality product with less coloring.
Description
【０００１】[0001]
【産業上の利用分野】本発明は（メタ）アクリル酸の重
合防止方法に関するものである。更に詳しくはアクリル
酸またはメタクリル酸の精製、貯蔵もしくは輸送中また
はエステル化反応時に、重合防止剤として、特定のＮ−
オキシル化合物と、フェノチアジン、芳香族アミン類、
フェノール類化合物の一種以上とを共存させることを特
徴とする（メタ）アクリル酸の重合防止方法に関するも
のである。FIELD OF THE INVENTION The present invention relates to a method for preventing polymerization of (meth) acrylic acid. More specifically, during the purification, storage or transportation of acrylic acid or methacrylic acid, or during the esterification reaction, a specific N-
Oxyl compound, phenothiazine, aromatic amines,
The present invention relates to a method for preventing polymerization of (meth) acrylic acid, which comprises allowing one or more phenol compounds to coexist.
【０００２】[0002]
【従来の技術】（メタ）アクリル酸は、極めて重合しや
すく、製造工程、貯蔵もしくは輸送中またはエステル化
反応に使用する際に、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。It is known that (meth) acrylic acid is extremely easy to polymerize, and often causes polymerization trouble due to heat, light, or other factors during the manufacturing process, storage or transportation, or when used in an esterification reaction. Has been.
【０００３】従来から、（メタ）アクリル酸用の重合抑
制剤として、フェノチアジン、フェニレンジアミン等の
芳香族アミン類、ハイドロキノン及びその誘導体等のフ
ェノール類化合物が知られている。Conventionally, as a polymerization inhibitor for (meth) acrylic acid, aromatic amines such as phenothiazine and phenylenediamine, and phenol compounds such as hydroquinone and its derivatives are known.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
の化合物は重合抑制剤としての能力が不十分であった
り、高価である等の問題を有していた。さらに（メタ）
アクリル酸のモノマーとしての貯蔵安定性を確保するた
め多量に添加した場合には、着色の原因になったり、ま
た蒸留操作によってのみ、重合抑制剤の除去が可能であ
り、その除去は容易でなかった。またα，β−不飽和カ
ルボン酸エステル類のポップコ−ン重合禁止剤として、
Ｎ−オキシル化合物を用いる（特公昭５８−４６４９６
号公報）ことが、さらにα，β−不飽和カルボン酸エス
テル類の重合禁止剤として、２，２，６，６−テトラメ
チル化合物を使用する（特公平４−１４１２１号公報）
ことが提案されているが、これらの化合物の（メタ）ア
クリル酸の重合抑制剤としての効果は不十分であった。However, these compounds have problems such as insufficient ability as a polymerization inhibitor and high cost. Furthermore (meta)
When a large amount of acrylic acid is added to ensure storage stability as a monomer, it may cause coloration, and the polymerization inhibitor can be removed only by distillation operation, and its removal is not easy. It was Further, as a popcorn polymerization inhibitor of α, β-unsaturated carboxylic acid esters,
N-oxyl compound is used (Japanese Patent Publication No. 58-46496).
Further, a 2,2,6,6-tetramethyl compound is used as a polymerization inhibitor for α, β-unsaturated carboxylic acid esters (Japanese Patent Publication No. 4-14121).
However, the effect of these compounds as a polymerization inhibitor of (meth) acrylic acid was insufficient.
【０００５】本発明者らは、前記の問題点を克服すべ
く、鋭意検討した結果、本発明に到達した。The present inventors have arrived at the present invention as a result of intensive studies to overcome the above problems.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上記のα，
β−不飽和カルボン酸エステル類の重合禁止剤として、
２，２，６，６−テトラメチル化合物のα，β−不飽和
カルボン酸エステル類の重合抑制効果に着目し、それを
（メタ）アクリル酸の重合抑制に利用する方法について
鋭意検討した結果、２，２，６，６−テトラメチルピペ
リジン基を有するＮ−オキシル化合物と、フェノチアジ
ン、芳香族アミン類、フェノール類化合物を共存させる
ことにより、（メタ）アクリル酸の予期せぬ重合抑制効
果を有することを見出だし、本発明を完成するに至っ
た。The present inventors have proposed the above α,
As a polymerization inhibitor of β-unsaturated carboxylic acid esters,
Focusing on the polymerization inhibiting effect of the α, β-unsaturated carboxylic acid esters of the 2,2,6,6-tetramethyl compound, as a result of diligent study on a method of utilizing it for inhibiting the polymerization of (meth) acrylic acid, Coexistence of an N-oxyl compound having a 2,2,6,6-tetramethylpiperidine group with a phenothiazine, an aromatic amine, or a phenol compound has an unexpected polymerization inhibitory effect on (meth) acrylic acid. They found out that, and completed the present invention.
【０００７】即ち、本発明は、（メタ）アクリル酸の精
製時、貯蔵もしくは輸送時またはエステル化反応時に、
重合防止剤として、下記一般式（１）で表されるＮ−オ
キシル化合物と、フェノチアジン、芳香族アミン類、フ
ェノール類化合物の一種以上とを共存させることを特徴
とする（メタ）アクリル酸の重合防止方法である。That is, the present invention relates to (meth) acrylic acid during purification, storage or transportation, or esterification reaction.
Polymerization of (meth) acrylic acid, characterized in that an N-oxyl compound represented by the following general formula (1) and one or more of phenothiazine, aromatic amines, and phenol compounds coexist as a polymerization inhibitor. It is a prevention method.
【化２】 ただし一般式（１）において、Ｒは水素原子、アルキル
基、アシル基を示す。[Chemical 2] However, in the general formula (1), R represents a hydrogen atom, an alkyl group, or an acyl group.
【０００８】本発明に用いられる（メタ）アクリル酸と
は、アクリル酸またはメタクリル酸であり、どのような
製法により製造された（メタ）アクリル酸にも用いるこ
とができる。The (meth) acrylic acid used in the present invention is acrylic acid or methacrylic acid, and can be used for (meth) acrylic acid produced by any production method.
【０００９】本発明で使用されるＮ−オキシル化合物
は、下記一般式（１）で表されるものである。The N-oxyl compound used in the present invention is represented by the following general formula (1).
【化３】 ただし一般式（１）において、Ｒは水素原子、アルキル
基、アシル基を示す。そのうち適切なものは、Ｒが水素
原子、炭素数１〜６のアルキル基、炭素数１〜８のアシ
ル基を有する化合物であり、特に２，２，６，６−テト
ラメチル−４−アセトキシピペリジン−１−オキシル、
２，２，６，６−テトラメチル−４−ヒドロキシピペリ
ジン−１−オキシルまたは２，２，６，６−テトラメチ
ル−４−メトキシピペリジン−１−オキシル等が望まし
く、その使用量は（メタ）アクリル酸モノマ−に対して
０．０００１〜０．０５重量％、好ましくは０．０００
１〜０．０１重量％である。[Chemical 3] However, in the general formula (1), R represents a hydrogen atom, an alkyl group, or an acyl group. Suitable among them are compounds in which R has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an acyl group having 1 to 8 carbon atoms, particularly 2,2,6,6-tetramethyl-4-acetoxypiperidine. -1-oxyl,
2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl or 2,2,6,6-tetramethyl-4-methoxypiperidine-1-oxyl is desirable, and the amount thereof is (meth) 0.0001 to 0.05% by weight, preferably 0.000, relative to acrylic acid monomer
It is 1 to 0.01% by weight.
【００１０】Ｎ−オキシル化合物と共存使用する重合抑
制剤としてフェノチアジン、芳香族アミン類、フェノー
ル類等があるが、具体的には、フェノチアジン（ＰＴ
Ｚ）、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（ＨＱ）、ハイドロキノンモノメチルエー
テル（メトキノンＭＱ）があり、その一種以上がもちい
られ、その使用量は０．０００１〜０．０５重量％、好
ましくは０．０００１〜０．０３重量％である。この重
合防止剤は、（メタ）アクリル酸とメタノール、エタノ
ール、ブタノール、２−エチルヘキサノール、エチレン
オキサイド、ステアリルアルコール、トリブチル錫オキ
サイド等との反応にも使用される。その際、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が
使用されるが特に制限はない。Examples of the polymerization inhibitor used together with the N-oxyl compound include phenothiazine, aromatic amines and phenols. Specifically, phenothiazine (PT
Z), p-phenylenediamine, diphenylamine, hydroquinone (HQ) and hydroquinone monomethyl ether (methoquinone MQ), one or more of which are used, and the amount thereof is 0.0001 to 0.05% by weight, preferably 0. It is 0001 to 0.03% by weight. This polymerization inhibitor is also used in the reaction of (meth) acrylic acid with methanol, ethanol, butanol, 2-ethylhexanol, ethylene oxide, stearyl alcohol, tributyltin oxide and the like. At that time, sulfuric acid, p-toluenesulfonic acid, a cation exchange resin or the like is used as a catalyst, but there is no particular limitation.
【００１１】また、本発明の使用雰囲気は、窒素等の不
活性ガス下でも有効であるが、（メタ）アクリル酸の精
製時およびエステル反応使用時においては、酸素の存在
下で使用する方が有効である。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具体例として挙げら
れる。The atmosphere of use of the present invention is also effective under an inert gas such as nitrogen, but it is better to use it in the presence of oxygen during the purification of (meth) acrylic acid and the ester reaction. It is valid. As a method of supplying oxygen in this case, an air bubbling method can be given as a specific example.
【００１２】さらに、実施例で示すように、本発明の重
合防止能力は、従来のものより格段に優れており、使用
する場合もその添加量を大幅に削減することが可能とな
る。それ故、着色も少なくなり、特に貯蔵安定剤として
用いる場合には、除去操作も必要としない。Further, as shown in the examples, the polymerization preventing ability of the present invention is far superior to that of the conventional one, and even when it is used, the addition amount thereof can be greatly reduced. Therefore, the coloring is reduced, and the removal operation is not required especially when used as a storage stabilizer.
【００１３】また、本発明で使用するＮ−オキシル化合
物は、既知物質で毒性も低く、重金属を含有しない化合
物であるため、環境汚染の問題もない。Further, since the N-oxyl compound used in the present invention is a known substance and has low toxicity and does not contain heavy metals, there is no problem of environmental pollution.
【００１４】本発明を実施する事により、従来技術の欠
点を解決する事が可能となり、その工業的意義は極めて
大きいものと思われる。By carrying out the present invention, it becomes possible to solve the drawbacks of the prior art, and it is considered that its industrial significance is extremely great.
【００１５】[0015]
【実施例】次に実施例により、具体的に説明するが、こ
れらは、本発明を限定するものではない。なお、以下の
例において、％、ppm 、はいずれも重量％、重量ppm 、
を示すものである。EXAMPLES The present invention will now be specifically described with reference to examples, but these do not limit the present invention. In the following examples,% and ppm are all% by weight, ppm by weight,
Is shown.
【００１６】（実験手法） 重合誘導期（ＩＰ）の測定；重合防止剤の効果を判定す
るために、（メタ）アクリル酸モノマーが重合に至まで
の誘導期の測定を行った。すなわち所定量の添加物を含
有する（メタ）アクリル酸を調製し、その５mlを試験官
に採り、シリコンゴム栓で密封した後、アクリル酸の場
合、１００℃、メタクリル酸の場合、１１０℃の油浴中
に浸し、重合開始に伴って当該サンプルに濁りが発生す
るまでの時間を測定する。こうして得られた重合に至る
までの誘導期をＩＰ−１００（アクリル酸の場合）、ま
たはＩＰ−１１０（メタクリル酸の場合）と略記して、
時間の単位で表わした。(Experimental Method) Measurement of polymerization induction period (IP): In order to determine the effect of the polymerization inhibitor, the induction period until the (meth) acrylic acid monomer was polymerized was measured. That is, (meth) acrylic acid containing a predetermined amount of additive was prepared, and 5 ml thereof was taken by a tester and sealed with a silicone rubber stopper. After that, 100 ° C for acrylic acid and 110 ° C for methacrylic acid. Immerse in an oil bath, and measure the time until turbidity occurs in the sample with the start of polymerization. The induction period until the polymerization thus obtained is abbreviated as IP-100 (in the case of acrylic acid) or IP-110 (in the case of methacrylic acid),
Expressed in units of time.
【００１７】（実施例１）メタクリル酸に、２，２，
６，６−テトラメチル−４−アセトキシピペリジン−１
−オキシル１０ppm と、メトキノン（ＭＱ）５０ppm を
添加してＩＰ−１１０を測定した結果、２５．０時間で
あった。Example 1 Methacrylic acid was added to 2, 2,
6,6-Tetramethyl-4-acetoxypiperidine-1
-Oxyl (10 ppm) and metquinone (MQ) (50 ppm) were added, and IP-110 was measured. As a result, it was 25.0 hours.
【００１８】（比較例１）実施例１で使用したメタクリ
ル酸に２，２，６，６−テトラメチル−４−アセトキシ
ピペリジン−１−オキシル１０ppm のみを添加した場合
のＩＰ−１１０は１．８時間であった。(Comparative Example 1) The IP-110 obtained by adding 10 ppm of 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl to the methacrylic acid used in Example 1 was 1.8. It was time.
【００１９】（比較例２）実施例１で使用したメタクリ
ル酸にメトキノン（ＭＱ）５０ppm のみを添加した場合
のＩＰ−１１０は２．１時間であった。Comparative Example 2 IP-110 was 2.1 hours when only 50 ppm of methquinone (MQ) was added to the methacrylic acid used in Example 1.
【００２０】（実施例２）メタクリル酸に、２，２，
６，６−テトラメチル−４−アセトキシピペリジン−１
−オキシル１０ppm と、フエノチアジン（ＰＴＺ）５０
ppm を添加してＩＰ−１１０を測定した結果、２８．１
時間であった。Example 2 Methacrylic acid was added to 2, 2,
6,6-Tetramethyl-4-acetoxypiperidine-1
-Oxyl 10ppm and phenothiazine (PTZ) 50
As a result of measuring IP-110 by adding ppm, 28.1
It was time.
【００２１】（比較例３）実施例２において、フエノチ
アジン（ＰＴＺ）５０ppm のみを添加してＩＰ−１１０
を測定した結果、２．２時間であった。(Comparative Example 3) In Example 2, IP-110 was prepared by adding only 50 ppm of phenothiazine (PTZ).
As a result, it was 2.2 hours.
【００２２】（実施例３〜７）実施例１と同じメタクリ
ル酸を用いて（表１）に示す重合防止剤を添加した時の
ＩＰ−１１０を測定した。結果を（表１）にまとめて示
す。(Examples 3 to 7) Using the same methacrylic acid as in Example 1, IP-110 was measured when the polymerization inhibitor shown in (Table 1) was added. The results are summarized in (Table 1).
【００２３】 （表１） 実施例 Ｎ−オキシル化合物 重合防止剤 ＩＰ−１１０ （ppm) （ppm) （hrs) ３ Ｒ＝Ｈ ＭＱ ８．４ ５ ５０ ４ Ｒ＝ＣＨ3 ＰＴＺ １０．５ ５ ５０ ５ Ｒ＝ＣＯＣＨ3 Ｐ−フェニレン １１．８ １０ ジアミン ５０ ６ Ｒ＝ＣＯＰｈ 同上 ８．５ １５ ５０ ７ Ｒ＝Ｃ2 Ｈ5 ＰＴＺ ７．４ １５ ５０(Table 1) Example N-oxyl compound Polymerization inhibitor IP-110 (ppm) (ppm) (hrs) 3 R = H MQ 8.4 5 50 4 R = CH 3 PTZ 10.5 5 50 5 R = COCH 3 P-phenylene 11.8 10 diamine 50 6 R = COPh ibid 8.5 15 50 7 R = C 2 H 5 PTZ 7.4 15 50
【００２４】（実施例８）実施例１で用いたメタクリル
酸１００mlを減圧蒸留装置に入れ、２，２，６，６−テ
トラメチル−４−アセトキシピペリジン−１−オキシル
を５．０ppm 、ＰＴＺを３０ppm 添加して、９５℃で全
環流を１０時間実施した。冷却した後のメタクリル酸の
外観は透明で、ポリマーの生成による濁りは認められな
かった。(Example 8) 100 ml of methacrylic acid used in Example 1 was put into a vacuum distillation apparatus, 5.0 ppm of 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl and PTZ were added. After adding 30 ppm, total reflux was carried out at 95 ° C. for 10 hours. The appearance of methacrylic acid after cooling was transparent and no turbidity due to polymer formation was observed.
【００２５】（比較例５）実施例８と同様の装置、条件
で、２，２，６，６−テトラメチル−４−アセトキシピ
ペリジン−１−オキシルを添加しないメタクリル酸の全
環流を５時間実施した。冷却後のメタクリル酸にはポリ
マーによる濁りの発生が確認された。(Comparative Example 5) Using the same apparatus and conditions as in Example 8, a total reflux of methacrylic acid was carried out for 5 hours without adding 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl. did. It was confirmed that polymer turbidity was generated in methacrylic acid after cooling.
【００２６】（実施例９）アクリル酸に、２，２，６，
６−テトラメチル−４−アセトキシピペリジン−１−オ
キシル１０ppm と、メトキノン（ＭＱ）１５０ppm を添
加してＩＰ−１００を測定した結果、１６．６時間であ
った。Example 9 Acrylic acid was added to 2, 2, 6,
As a result of adding 10 ppm of 6-tetramethyl-4-acetoxypiperidine-1-oxyl and 150 ppm of methquinone (MQ) and measuring IP-100, it was 16.6 hours.
【００２７】（比較例６）実施例９で、２，２，６，６
−テトラメチル−４−アセトキシピペリジン−１−オキ
シルを添加しない場合のＩＰ−１００は１．２時間であ
った。(Comparative Example 6) In Example 9, 2, 2, 6, 6
-IP-100 without the addition of tetramethyl-4-acetoxypiperidine-1-oxyl was 1.2 hours.
【発明の効果】本発明の重合防止方法は、複合型重合抑
制剤を共存させる事により、（メタ）アクリル酸の精製
時、貯蔵もしくは輸送時およびエステル化反応時に問題
となる重合物発生を防止する事ができる。さらに重合防
止剤の添加量を削減することが可能となり、着色のより
少ない高品質の製品を得る事ができる、非常に有用な重
合防止方法である。EFFECTS OF THE INVENTION The polymerization preventing method of the present invention prevents the generation of a polymer, which is a problem during the purification, storage or transportation of (meth) acrylic acid and during the esterification reaction, by allowing a complex type polymerization inhibitor to coexist. You can do it. Furthermore, the addition amount of the polymerization inhibitor can be reduced, and a high-quality product with less coloring can be obtained, which is a very useful polymerization prevention method.
Claims (3)
くは輸送時またはエステル化反応時に、重合防止剤とし
て、下記一般式（１）で表されるＮ−オキシル化合物
と、フェノチアジン、芳香族アミン類、フェノール類化
合物の一種以上とを共存させることを特徴とする（メ
タ）アクリル酸の重合防止方法。 【化１】 ただし一般式（１）において、Ｒは水素原子、アルキル
基、アシル基を示す。1. An N-oxyl compound represented by the following general formula (1), a phenothiazine, and an aromatic amine as a polymerization inhibitor during purification, storage or transportation of (meth) acrylic acid, or during esterification reaction. And a method for preventing polymerization of (meth) acrylic acid, which comprises coexisting with at least one of phenols and phenol compounds. [Chemical 1] However, in the general formula (1), R represents a hydrogen atom, an alkyl group, or an acyl group.
素数１〜６のアルキル基、炭素数１〜８のアシル基で表
されるＮ−オキシル化合物である請求項１記載の（メ
タ）アクリル酸の重合防止方法。2. R-in the general formula (1) is an N-oxyl compound represented by a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 1 to 8 carbon atoms (meta) ) A method for preventing polymerization of acrylic acid.
テトラメチル−４−アセトキシピペリジン−１−オキシ
ル、２，２，６，６−テトラメチル−４−ヒドロキシピ
ペリジン−１−オキシルまたは２，２，６，６−テトラ
メチル−４−メトキシピペリジン−１−オキシルである
請求項１記載の（メタ）アクリル酸の重合防止方法。3. The N-oxyl compound is 2,2,6,6-
Tetramethyl-4-acetoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl or 2,2,6,6-tetramethyl-4-methoxypiperidine-1- The method for preventing polymerization of (meth) acrylic acid according to claim 1, which is oxyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15451992A JP3227204B2 (en) | 1992-05-21 | 1992-05-21 | Method for preventing polymerization of (meth) acrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15451992A JP3227204B2 (en) | 1992-05-21 | 1992-05-21 | Method for preventing polymerization of (meth) acrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05320217A true JPH05320217A (en) | 1993-12-03 |
| JP3227204B2 JP3227204B2 (en) | 2001-11-12 |
Family
ID=15586032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15451992A Expired - Lifetime JP3227204B2 (en) | 1992-05-21 | 1992-05-21 | Method for preventing polymerization of (meth) acrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3227204B2 (en) |
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| JPH09194515A (en) * | 1996-01-12 | 1997-07-29 | Ivoclar Ag | Photosetting composite material |
| WO1999007664A1 (en) * | 1997-08-07 | 1999-02-18 | Basf Aktiengesellschaft | Process for stabilising (metha)acrylic acid esters against unwanted radical polymerisation |
| US5888356A (en) * | 1994-08-19 | 1999-03-30 | Huels Aktiengesellschaft | Inhibition of polymerization of vinylaromatic or vinylaliphatic |
| US5932735A (en) * | 1997-06-13 | 1999-08-03 | Ciba Specialty Chemicals Corporation | Derivatives of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth)acrylate monomers |
| WO2000003965A1 (en) | 1998-07-14 | 2000-01-27 | Ciba Specialty Chemicals Holding Inc. | Derivatives of 1-oxyl-4-hydroxy- or 4-amino-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth)acrylate monomers |
| JP2000169429A (en) * | 1998-12-10 | 2000-06-20 | Mitsubishi Rayon Co Ltd | Production of high-purity (meth)acrylic ester |
| JP2000514451A (en) * | 1996-07-15 | 2000-10-31 | エー．エッチ．マークス アンド カンパニー リミテッド | Polymerization inhibitor |
| JP2001521046A (en) * | 1997-10-29 | 2001-11-06 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for immediate termination of radical polymerization and its apparatus, inhibitor solution, and ship equipped with the apparatus |
| US6337426B1 (en) | 1998-11-23 | 2002-01-08 | Nalco/Exxon Energy Chemicals, L.P. | Antifoulant compositions and processes |
| JP2003522777A (en) * | 2000-02-17 | 2003-07-29 | デンツプライ インターナショナル インコーポレーテッド | Light-stable dental composition |
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| WO1999007664A1 (en) * | 1997-08-07 | 1999-02-18 | Basf Aktiengesellschaft | Process for stabilising (metha)acrylic acid esters against unwanted radical polymerisation |
| JP2001521046A (en) * | 1997-10-29 | 2001-11-06 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for immediate termination of radical polymerization and its apparatus, inhibitor solution, and ship equipped with the apparatus |
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| JP2000169429A (en) * | 1998-12-10 | 2000-06-20 | Mitsubishi Rayon Co Ltd | Production of high-purity (meth)acrylic ester |
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