JP2010090060A - Alkenyloxazoline - Google Patents
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Abstract
Description
本発明は、アルケニルオキサゾリンについて、貯蔵時又は輸送の間の増粘、着色などの変質を防止でき、長期間保存安定性を付与し、且つ重合性を低下させない方法に関するものである。また、当該方法により安定化されたアルケニルオキサゾリンに関するものである。 The present invention relates to a method for preventing alkenyloxazoline from being deteriorated during storage or transportation, such as thickening and coloring, imparting long-term storage stability, and not degrading the polymerizability. The present invention also relates to an alkenyl oxazoline stabilized by the method.
アルケニルオキサゾリンは、分子中に重合性のビニル基と反応性のオキサゾリン基を有するニ官能モノマーであり、機能性モノマーとして注目されている。特に最近は、オキサゾリン基がカルボキシル基、酸無水物、フェノール性水酸基、チオール基、アミノ基、アミド基、スルフィン酸基、エポキシ基など種々の官能基に対して良好な反応性を有し、また反応に伴い副生成物を発生しないことから、環境対応型樹脂相溶化剤、樹脂加水分解抑制剤、塗料、粘接着剤、架橋剤の原料として、その製造方法と用途開発の研究が盛んに行われている（非特許文献１〜１０及び特許文献１〜２）。 Alkenyl oxazoline is a bifunctional monomer having a polymerizable vinyl group and a reactive oxazoline group in the molecule, and has attracted attention as a functional monomer. Particularly recently, oxazoline groups have good reactivity with various functional groups such as carboxyl groups, acid anhydrides, phenolic hydroxyl groups, thiol groups, amino groups, amide groups, sulfinic acid groups, and epoxy groups. Since no by-products are generated with the reaction, research on production methods and application development as raw materials for environmentally compatible resin compatibilizers, resin hydrolysis inhibitors, paints, adhesives, and crosslinking agents (Non-patent documents 1 to 10 and Patent documents 1 and 2).
一方、アルケニルオキサゾリンは易重合性、高反応性、高い浸透性を有する化合物で、貯蔵及び輸送中に増粘や着色を起こすことをあり、それらの安定性向上が大きな課題となっている。
アルケニルオキサゾリンの製造工程での重合防止については、ハイドロキノン、ｐ−メトキシフェノールとフェノチアジンなどビニルモ ノマー用の一般的な重合禁止剤の添加が提案されてきた（特許文献３〜８）。本発明者らは、これらの重合禁止剤をアルケニルオキサゾリンの貯蔵及び輸送中における保存安定剤としても用いることを検討し研究を行った。しかしながら、これらの重合禁止剤はアルケニルオキサゾリンの早期重合による増粘、着色の抑制に必ずしも適したものではなく、又はモノマー本来の重合反応性を低下させることが多かった。
また、ヒドロキシルアミン化合物であるＮ−ニトロソフェニルヒドロキシルアミンやＮ−フェニルヒドロキシルアミンも、重合禁止剤として一般的に用いられるものであるが、Ｎ−ニトロソフェニルヒドロキシルアミンもしくはそのアンモニウム塩をアルケニルオキサゾリンに添加すると着色を促進してしまい、Ｎ−フェニルヒドロキシルアミンはアルケニルオキサゾリンのビニル基とマイケル付加することがあるため、いずれも保存安定剤としては適さない。
On the other hand, alkenyl oxazoline is a compound having high polymerizability, high reactivity, and high penetrability, which may cause thickening and coloring during storage and transportation, and improving their stability is a major issue.
Regarding the prevention of polymerization in the production process of alkenyl oxazoline, the addition of general polymerization inhibitors for vinyl monomers such as hydroquinone, p-methoxyphenol and phenothiazine has been proposed (Patent Documents 3 to 8). The present inventors have studied and studied the use of these polymerization inhibitors as storage stabilizers during storage and transportation of alkenyl oxazolines. However, these polymerization inhibitors are not necessarily suitable for suppression of thickening and coloration due to premature polymerization of alkenyl oxazoline, or often reduce the original polymerization reactivity of the monomer.
In addition, N-nitrosophenylhydroxylamine and N-phenylhydroxylamine, which are hydroxylamine compounds, are generally used as polymerization inhibitors, but N-nitrosophenylhydroxylamine or its ammonium salt is added to alkenyl oxazoline. Then, coloring is promoted, and N-phenylhydroxylamine may be Michael-added to the vinyl group of alkenyl oxazoline, so that neither is suitable as a storage stabilizer.
本発明の課題は、貯蔵中及び輸送中の増粘や着色などの変質が防止され、長期間安定的に保存できるアルケニルオキサゾリンを提供することにある。また、アルケニルオキサゾリンに適用する保存安定剤及びアルケニルオキサゾリンの安定化方法を提供することにある。 An object of the present invention is to provide an alkenyl oxazoline which can be stably stored for a long period of time while preventing alteration such as thickening and coloring during storage and transportation. Another object of the present invention is to provide a storage stabilizer applied to alkenyl oxazoline and a method for stabilizing alkenyl oxazoline.
本発明者らは、かかる課題を解決するために鋭意検討を重ねた結果、Ｎ，Ｎ−ジアルキルヒドロキシルアミンとＮ，Ｎ−ジアリールヒドロキシルアミンがアルケニルオキサゾリンに対して優れた早期重合と着色の防止効果を有することを見出し、本発明を完成するに至った。
すなわち本発明は、
（１）保存安定剤としてヒドロキシルアミン化合物を含有する、一般式［１］（式中、Ｒ1は水素原子またはメチル基を、Ｒ2〜Ｒ5は同一または異なって水素原子または炭素数１〜３の低級アルキル基を表す。）で表されるアルケニルオキサゾリンであって、前記ヒドロキシルアミン化合物が一般式［２］（式中、Ａは炭素数１〜１２のアルキル基もしくはシクロアルキル基、または炭素数６〜９のアリール基を表す。）で表されるＮ，Ｎ−ジアルキルヒドロキシルアミンまたはＮ，Ｎ−ジアリールヒドロキシルアミンであることを特徴とする、アルケニルオキサゾリン。
（３）一般式［１］（式中、Ｒ1は水素原子またはメチル基を、Ｒ2〜Ｒ5は同一または異なって水素原子または炭素数１〜３の低級アルキル基を表す。）で表されるアルケニルオキサゾリンに、保存安定剤として一般式［２］（式中、Ａは炭素数１〜１２のアルキル基またはシクロアルキル基、または炭素数６〜９のアリール基を表す。）で表されるＮ，Ｎ−ジアルキルヒドロキシルアミンまたはＮ，Ｎ−ジアリールヒドロキシルアミンを添加することを特徴とする、前記アルケニルオキサゾリンの貯蔵時または輸送時における安定化法。
That is, the present invention
(1) General formula [1] containing a hydroxylamine compound as a storage stabilizer, wherein R 1 is a hydrogen atom or a methyl group, and R 2 to R 5 are the same or different and have a hydrogen atom or a carbon number of 1 to Wherein the hydroxylamine compound is represented by the general formula [2] (wherein A is an alkyl or cycloalkyl group having 1 to 12 carbon atoms, or carbon. An alkenyloxazoline, which is an N, N-dialkylhydroxylamine or N, N-diarylhydroxylamine represented by formula (6) to (9).
(3) Represented by the general formula [1] (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 to R 5 are the same or different and represent a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms). The alkenyl oxazoline is represented by the general formula [2] as a storage stabilizer (wherein A represents an alkyl or cycloalkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 9 carbon atoms). N, N-dialkylhydroxylamine or N, N-diarylhydroxylamine is added. A method for stabilizing the alkenyloxazoline during storage or transportation.
本発明によれば、貯蔵中及び輸送中の増粘や着色などの変質が少なく、長期間保存安定性を有し、且つ重合性が低下せず、求める重合体を製造できる一般式［１］で表されるアルケニルオキサゾリンが提供される。 According to the present invention, the general formula [1] that can produce the desired polymer with little deterioration during storage and transportation such as thickening and coloring, long-term storage stability, and no decrease in polymerizability. The alkenyl oxazoline represented by these is provided.
本発明のアルケニルオキサゾリンは、保存安定剤としてヒドロキシルアミン化合物を含有する、一般式［１］で表されるアルケニルオキサゾリンである。
本発明で用いられるアルケニルオキサゾリンは、本発明者等が先に出願した特許文献３〜７に記載の方法で製造できる。 The alkenyl oxazoline used in the present invention can be produced by the methods described in Patent Documents 3 to 7 previously filed by the present inventors.
本発明のヒドロキシルアミン化合物は、一般式［２］で表されるＮ，Ｎ−ジアルキルヒドロキシルアミンとＮ，Ｎ−ジアリールヒドロキシルアミンである。
これらのヒドロキシルアミンは、１種あるいは２種以上を用いることができ、また、Ｎ，Ｎ−ジアルキルヒドロキシルアミンとＮ，Ｎ−ジアリールヒドロキシルアミンの混合物を使用することもできる。安全性が高い点と高純度の工業品が容易に入手できる点で、Ｎ，Ｎ−ジフェニルヒドロキシルアミンとＮ，Ｎ−ジベンジルヒドロキシルアミンが好ましい。
The hydroxylamine compound of the present invention is N, N-dialkylhydroxylamine and N, N-diarylhydroxylamine represented by the general formula [2].
These hydroxylamines can be used alone or in combination of two or more, and a mixture of N, N-dialkylhydroxylamine and N, N-diarylhydroxylamine can also be used. N, N-diphenylhydroxylamine and N, N-dibenzylhydroxylamine are preferred in terms of high safety and easy availability of high-purity industrial products.
本発明に用いるヒドロキシルアミン化合物の添加量は、アルケニルオキサゾリンの保存条件又は保存期間等により最適使用量は変化するが、通常、アルケニルオキサゾリンに対して、重量比で０．１ｐｐｍ〜１００００ｐｐｍ、好ましくは１ｐｐｍ〜１０００ｐｐｍ、より好ましくは１０ｐｐｍ〜１００ｐｐｍである。
ヒドロキシルアミン化合物の添加量が０．１ｐｐｍ未満では、十分な効果が発揮されない場合がある。また、ヒドロキシルアミン化合物の添加量が１００００ｐｐｍ以上では、十分な保存安定性は得られるが、アルケニルオキサゾリンの重合体製造時に高分子量品が生成しにくくなる可能性がある。
The optimum amount of the hydroxylamine compound used in the present invention varies depending on the storage conditions or storage period of the alkenyl oxazoline, but usually 0.1 ppm to 10,000 ppm, preferably 1 ppm by weight with respect to the alkenyl oxazoline. ˜1000 ppm, more preferably 10 ppm to 100 ppm.
If the amount of the hydroxylamine compound added is less than 0.1 ppm, sufficient effects may not be exhibited. Further, when the amount of the hydroxylamine compound added is 10,000 ppm or more, sufficient storage stability can be obtained, but it may be difficult to produce a high molecular weight product during the production of the alkenyloxazoline polymer.
本発明に用いるヒドロキシルアミン化合物は、他成分例えば他の一般的に使用されている公知の重合防止剤を混合してもよい。一般的な重合防止剤のなかで、ハイドロキノン、ハイドロキノンモノメチルエーテル、ベンゾキノン、ｐ−ｔｅｒｔ−ブチルカテコール、フェノチアジン、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、１，４−ジヒドロキシ−２，２，６，６−テトラメチルピペリジン、１−ヒドロキシ−４−ベンゾイリオキシ−２，２，６，６−テトラメチルピペリジン、２，２，６，６−テトラメチルピペリジン−Ｎ−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−Ｎ−オキシル、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシルが好適に用いられる。これらの重合禁止剤は、単独でも、あるいは２種以上を適宜組み合わせて使用することができる。 The hydroxylamine compound used in the present invention may be mixed with other components such as other commonly used polymerization inhibitors. Among general polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2, 2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetra Methylpiperidine-N-oxyl is preferably used. These polymerization inhibitors can be used alone or in appropriate combination of two or more.
本発明に用いるヒドロキシルアミンは、他の一般的な重合防止剤と同様、アルケニルオキサゾリンに対して一般的な方法で添加することができる。また、ヒドロキシルアミンと他の一般的な重合防止剤を併用する場合、これらの添加は同時でも別々でもよい。 The hydroxylamine used in the present invention can be added in a general manner to alkenyl oxazoline as well as other general polymerization inhibitors. Moreover, when using together hydroxylamine and another general polymerization inhibitor, these addition may be simultaneous or separate.
本発明に用いるアルケニルオキサゾリンは、公知のラジカル重合法により単独重合、または他の共重合可能なビニル系単量体および／またはオリゴマーとの共重合を行うことができる。
他の共重合可能なビニル系単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、長鎖脂肪族（メタ）アクリレート、アリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどの（メタ）アクリレート系モノマー、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−プロピル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−ブチル（メタ）アクリルアミド、Ｎ−イソブチル（メタ）アクリルアミド、Ｎ−ペンチル（メタ）アクリルアミド、Ｎ−ヘキシル（メタ）アクリルアミド、Ｎ−へプチル（メタ）アクリルアミド、Ｎ−オクチル（メタ）アクリルアミド、Ｎ−ノニル（メタ）アクリルアミド、Ｎ−デシル（メタ）アクリルアミド、Ｎ−ドデシル（メタ）アクリルアミド、Ｎ−テトラデシル（メタ）アクリルアミド、Ｎ−ヘキサデシル（メタ）アクリルアミド、Ｎ−オレイル（メタ）アクリルアミド、Ｎ−ステアリル（メタ）アクリルアミド、Ｎ−エイコシル（メタ）アクリルアミド、Ｎ−ドコシル（メタ）アクリルアミド、Ｎ−エチルヘキシル（メタ）アクリルアミド、Ｎ−シクロヘキシル（メタ）アクリルアミド、Ｎ−イソボルニル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノエチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミドなどの（メタ）アクリルアミド系単量体、酢酸ビニル、（メタ）アクリロニトリル、スチレン等が例示される。
The alkenyl oxazoline used in the present invention can be homopolymerized by a known radical polymerization method or copolymerized with other copolymerizable vinyl monomers and / or oligomers.
Other copolymerizable vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, long chain aliphatic (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate , (Meth) acrylate monomers such as hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) ) Acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-pentyl (meth) acrylamide, N-hexyl (meth) acrylamide N-heptyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-decyl (meth) acrylamide, N-dodecyl (meth) acrylamide, N-tetradecyl (meth) acrylamide, N-hexadecyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-eicosyl (meth) acrylamide, N-docosyl (meth) acrylamide, N-ethylhexyl (me ) Acrylamide, N-cyclohexyl (meth) acrylamide, N-isobornyl (meth) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethylacrylamide, N, N-dimethylaminopropylacrylamide (Meth) acrylamide monomers such as vinyl acetate, (meth) acrylonitrile, styrene and the like.
アルケニルオキサゾリンの単独重合および他の共重合可能なビニル系単量体との共重合方法としては、特に限定されるものではなく、公知のラジカル重合法により実施可能である。
例えばアルコール、酢酸エチルなどの有機溶媒中の溶液重合、水溶液重合、懸濁重合、乳化重合、塊状重合法などが挙げられる。有機溶媒中の溶液重合法を採用する場合、重合溶媒としては、トルエン、キシレン、酢酸エチル、酢酸ブチル、メチルエチルケトン、メチルアルコール、エチルアルコールなどの単独もしくは混合で用いることができる。
The homopolymerization of alkenyl oxazoline and the copolymerization method with other copolymerizable vinyl monomers are not particularly limited, and can be carried out by a known radical polymerization method.
Examples thereof include solution polymerization in an organic solvent such as alcohol and ethyl acetate, aqueous solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. When the solution polymerization method in an organic solvent is employed, as a polymerization solvent, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl alcohol, ethyl alcohol, or the like can be used alone or in combination.
重合開始剤としては、アゾ系、有機過酸化物系、無機過酸化物系、レドックス系など一般的に知られている重合開始剤が挙げられる。重合開始剤の使用量としては、通常重合性単量体成分総量に対して０．００１〜１０重量％程度である。また、連鎖移動剤による分子量の調整など通常のラジカル重合技術が適用される。 Examples of the polymerization initiator include generally known polymerization initiators such as azo, organic peroxide, inorganic peroxide, and redox. As a usage-amount of a polymerization initiator, it is about 0.001 to 10 weight% normally with respect to the polymerizable monomer component total amount. Further, a normal radical polymerization technique such as adjustment of molecular weight by a chain transfer agent is applied.
以下に本発明の実施例について説明するが、本発明はこれら実施例に限定されるものではない。
＜アルケニルオキサゾリンの安定性に関する試験＞
実施例１〜５
２−ビニル−２−オキサゾリン（ＶＯＺＯ）４００ｇに保存安定剤として各種のヒドロキシルアミンを表１に示す割合で添加し、均一に溶解、混合した後、色相を測定し、初期値とした。１組成（実施例又は比較例）の混合液を５本の容量１００ｍLの蓋付き褐色ガラス製スクリュー管に８０ｍLずつ封入し、５点の安定性試験の試料を調製した。４０℃の恒温槽にそれらの試料を保存し、経時的に１点ずつ取り出し、室温に戻してからスクリュー管の蓋を開封し、内容物の色相を測定し、また目視で重合体生成による粘度増加の有無を調べた。結果を表１に示す。
Examples of the present invention will be described below, but the present invention is not limited to these examples.
<Test on stability of alkenyl oxazoline>
Examples 1-5
Various hydroxylamines as storage stabilizers were added to 400 g of 2-vinyl-2-oxazoline (VOZO) in the proportions shown in Table 1, and after uniformly dissolving and mixing, the hue was measured to obtain an initial value. 80 mL each of the mixed solution of one composition (Example or Comparative Example) was sealed in five brown glass screw tubes with caps having a capacity of 100 mL to prepare samples for five-point stability tests. The samples are stored in a constant temperature bath at 40 ° C., taken out one by one with time, returned to room temperature, the screw tube lid is opened, the hue of the contents is measured, and the viscosity due to polymer formation is visually observed. The presence or absence of an increase was examined. The results are shown in Table 1.
実施例６
実施例１において、保存安定剤をハイドロキノンモノメチルエーテルとジベンジルヒドロキシルアミンの混合物に変更した以外、実施例１と同様に実施した。条件と結果を表１に示す。
Example 6
The same operation as in Example 1 was performed except that the storage stabilizer was changed to a mixture of hydroquinone monomethyl ether and dibenzylhydroxylamine in Example 1. The conditions and results are shown in Table 1.
比較例１〜３
実施例１において、保存安定剤を無添加、ハイドロキノンモノメチルエーテル、フェノチアジンに変更した以外、実施例１と同様に実施した。条件と結果を表１に示す。
Comparative Examples 1-3
The same operation as in Example 1 was performed except that the storage stabilizer was not added, and hydroquinone monomethyl ether or phenothiazine was changed in Example 1. The conditions and results are shown in Table 1.
実施例７〜１０及び比較例４、５
実施例１及び比較例２において、２−ビニル−２−オキサゾリンの代わりに５−メチル−２−ビニル−２−オキサゾリン（ＭＶＯＺＯ）、４，４−ジメチル−２−ビニル−２−オキサゾリン（ＤＭＶＯＺＯ）、２−イソプロペニル−２−オキサゾリン（ＩＰＯＺＯ）を用い、実施例１及び比較例２と同様に実施した。条件と結果を表２に示す。
Examples 7 to 10 and Comparative Examples 4 and 5
In Example 1 and Comparative Example 2, 5-methyl-2-vinyl-2-oxazoline (MVOZO), 4,4-dimethyl-2-vinyl-2-oxazoline (DMVOZO) instead of 2-vinyl-2-oxazoline 2-Isopropenyl-2-oxazoline (IPOZO) was used in the same manner as in Example 1 and Comparative Example 2. The conditions and results are shown in Table 2.
＜アルケニルオキサゾリンの重合性に関する試験＞
試験例１〜６
撹拌装置、温度計、冷却器および乾燥窒素導入管を備えた容量５００ｍＬの反応容器に実施例１〜６で調製した本発明のヒドロキシルアミン配合ＶＯＺＯ１００ｇ（１．０３ｍｏｌ）、アゾビスイソブチロニトリル（ＡＩＢＮ）１．７ｇ（０．０１ｍｏｌ）と酢酸エチル１００ｍＬを仕込んだ。乾燥窒素気流下、反応液を３０℃で３０分攪拌した後、６０℃で８時間重合反応を行った。室温に戻した粘性高い反応液に酢酸エチル２００ｍＬを加え、均一に混合してからＢ型粘度計により粘度を測定した。また、ガスクロマトグラフ（ＧＣ）法で重合液中の残存モノマーを定量し、重合率を算出した。さらに、ゲルパーミエーションクロマトグラフ（ＧＰＣ）法で得られたポリマーの重量平均分子量を測定した（ポリスチレン標準物質）。結果を表３に示す。
なお、重合率は原料モノマーと残存モノマーの含量から下記式によって求めた。
<Test on Polymerizability of Alkenyloxazoline>
Test Examples 1-6
100 g (1.03 mol) of the hydroxylamine-containing VOZO prepared in Examples 1 to 6 and azobisisobutyronitrile (Example 3) were prepared in a reaction vessel having a capacity of 500 mL equipped with a stirrer, a thermometer, a condenser and a dry nitrogen introduction tube. AIBN) 1.7 g (0.01 mol) and ethyl acetate 100 mL were charged. The reaction solution was stirred at 30 ° C. for 30 minutes under a dry nitrogen stream, and then polymerized at 60 ° C. for 8 hours. 200 mL of ethyl acetate was added to the highly viscous reaction solution returned to room temperature and mixed uniformly, and then the viscosity was measured with a B-type viscometer. Moreover, the residual monomer in a polymerization liquid was quantified by the gas chromatograph (GC) method, and the polymerization rate was computed. Furthermore, the weight average molecular weight of the polymer obtained by the gel permeation chromatograph (GPC) method was measured (polystyrene standard substance). The results are shown in Table 3.
In addition, the polymerization rate was calculated | required by the following formula from the content of the raw material monomer and the residual monomer.
試験例７〜１０及び比較試験例１〜５
試験例１〜６において、実施例１〜６で調製した安定剤配合ＶＯＺＯの代わりに実験例７〜１０及び比較例１〜５で得られた各種アルケニルオキサゾリン混合液を用いた以外、試験例１〜６と同様に実施した。なお、ＡＩＢＮは各種アルケニルオキサゾリンに対して０．０１ｍｏｌになるように添加した。結果を表３に示す。
Test Examples 7 to 10 and Comparative Test Examples 1 to 5
In Test Examples 1 to 6, Test Example 1 except that the various alkenyloxazoline mixed solutions obtained in Experimental Examples 7 to 10 and Comparative Examples 1 to 5 were used in place of the stabilizer blend VOZO prepared in Examples 1 to 6. It carried out like -6. In addition, AIBN was added so that it might be set to 0.01 mol with respect to various alkenyl oxazolines. The results are shown in Table 3.
表１と表２に示した結果から明らかなように、本発明のヒドロキシルアミン化合物を配合した実施例１〜１０のアルケニルオキサゾリンは何れも安定剤無添加の比較例１及び一般的に使用されている公知の重合防止剤を添加した比較例２〜５よりも高い増粘防止効果、高い着色防止効果を有し、長期保存安定性において優れたものであった。これらのヒドロキシルアミン化合物はごく少量添加しても十分な効果を発揮でき、優れた安定性を有するアルケニルオキサゾリンが得られる。
また、表３の重合性試験の結果から、本発明のヒドロキシルアミン化合物の配合は、アルケニルオキサゾリンの保存安定性向上に有効であるのみでなく、重合特性も安定剤無添加系と比較して差がないことが明らかである。
一方、比較例２〜５及び比較試験例２〜５の結果から、一般的に使用されている公知の重合防止剤ＭＥＨＱ、ＴＤＡなどを多量添加した場合は、多少の増粘防止、着色防止効果があったが、長期保存性が不十分であった。さらに、公知の重合防止剤の使用による重合特性の低下は回避できないことも明らかであった。
As is apparent from the results shown in Tables 1 and 2, the alkenyl oxazolines of Examples 1 to 10 containing the hydroxylamine compound of the present invention are all used in Comparative Example 1 without addition of a stabilizer and generally used. It had a higher thickening prevention effect and a higher coloring prevention effect than Comparative Examples 2 to 5 to which a known polymerization inhibitor was added, and was excellent in long-term storage stability. Even if these hydroxylamine compounds are added in a very small amount, sufficient effects can be exerted, and alkenyloxazolines having excellent stability can be obtained.
Further, from the results of the polymerization test in Table 3, the formulation of the hydroxylamine compound of the present invention is not only effective for improving the storage stability of alkenyl oxazoline, but also has a difference in polymerization characteristics compared to the system without addition of a stabilizer. It is clear that there is no.
On the other hand, from the results of Comparative Examples 2 to 5 and Comparative Test Examples 2 to 5, when a large amount of commonly used polymerization inhibitors MEHQ, TDA, etc. are added, some thickening prevention and coloring prevention effects However, the long-term storage stability was insufficient. Furthermore, it was clear that a decrease in polymerization characteristics due to the use of known polymerization inhibitors cannot be avoided.
以上説明してきたように、保存安定剤として少量のＮ，Ｎ−二置換ヒドロキシルアミン化合物を配合することで、貯蔵時又は輸送の間に増粘、着色などの変質が起こらず、長期間保存安定性を有し、且つ重合性の低下しないアルケニルオキサゾリンが得られる。本発明のアルケニルオキサゾリンは環境対応型樹脂相溶化剤、樹脂加水分解抑制剤、塗料、粘接着剤、架橋剤などの原料として有用である。 As described above, by blending a small amount of N, N-disubstituted hydroxylamine compound as a storage stabilizer, the storage stability or long-term storage stability does not occur during storage or transportation, and no alteration such as thickening or coloring occurs. An alkenyl oxazoline that has the properties and does not lower the polymerizability is obtained. The alkenyl oxazoline of the present invention is useful as a raw material for environmentally friendly resin compatibilizers, resin hydrolysis inhibitors, paints, adhesives, crosslinking agents, and the like.
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| WO1999044972A1 (en) * | 1998-03-03 | 1999-09-10 | Nippon Zeon Co., Ltd. | Polymerization-inhibiting composition, polymerization inhibitor and method for inhibiting polymerization |
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