JP4400923B2 - 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) thioisocyanuric acid - Google Patents
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) thioisocyanuric acid Download PDFInfo
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Description
本発明は、化１で示される新規な１，３，５−トリス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)チオイソシアヌル酸に関するものである。 The present invention relates to a novel 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) thioisocyanuric acid represented by Chemical Formula 1.
プラスチックや合成ゴムなどの高分子材料は、成形加工時や成形後の製品の長期使用時に酸化を受け、機械的強度の低下や変色が発生する等の問題がある。このため、ホスホナイト系、ホスファイト系のリン系化合物やフェノール系化合物が、酸化防止剤として広く使用されている。
しかしながら、従来知られたこれらの酸化防止剤は、揮発性が高いために高分子材料に添加して成形加工される場合に揮散してしまい、十分な酸化防止効果が得られず、また高分子材料との相溶性に乏しいために、酸化防止剤が成形加工品の表面に滲出する（ブリードアウト）という問題があった。
Polymer materials such as plastics and synthetic rubbers suffer from problems such as deterioration in mechanical strength and discoloration due to oxidation during molding or long-term use of molded products. For this reason, phosphonite and phosphite phosphorus compounds and phenolic compounds are widely used as antioxidants.
However, these conventionally known antioxidants have high volatility, so they are volatilized when added to a polymer material and processed by molding, and a sufficient antioxidant effect cannot be obtained. Since the compatibility with the material is poor, there is a problem that the antioxidant oozes out on the surface of the molded product (bleed out).
また近年では、成形温度の高いエンジニヤリングプラスチックが使用されるに伴って、優れた熱安定性を有する酸化防止剤が求められている。
なお、本発明のチオイソシアヌル酸化合物に類似する酸化防止剤として、１，３，５−トリス（３，５−ジ−tert−ブチル−４−ヒドロキシベンジル）イソシアヌル酸が知られている（例えば、特許文献１）。
In recent years, as an engineering plastic having a high molding temperature is used, an antioxidant having excellent thermal stability has been demanded.
As an antioxidant similar to the thioisocyanuric acid compound of the present invention, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid is known (for example, Patent Document 1).
本発明は斯かる事情に鑑みてなされたものであって、上記の問題点を解決し得る酸化防止剤として有用な１，３，５−トリス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)チオイソシアヌル酸を提供することを目的とする。 The present invention has been made in view of such circumstances, and is useful for 1,3,5-tris (3,5-di-tert-butyl-4-methylate as an antioxidant capable of solving the above problems. The object is to provide hydroxybenzyl) thioisocyanuric acid.
本発明者は、前記の課題を解決するために鋭意検討を重ねた結果、化１で示される新規な１，３，５−トリス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)チオイソシアヌル酸を合成し得ることを認め、本発明を完成するに至ったものである。 As a result of intensive studies to solve the above problems, the present inventor has obtained a novel 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) represented by Chemical Formula 1 It has been recognized that thioisocyanuric acid can be synthesized, and the present invention has been completed.
本発明の１，３，５−トリス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)チオイソシアヌル酸は、高分子材料の酸化防止剤として有用なものである。 The 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) thioisocyanuric acid of the present invention is useful as an antioxidant for polymer materials.
以下、本発明について詳細に説明する。
本発明の１，３，５−トリス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)チオイソシアヌル酸は、化２の反応式に示されるとおり、チオシアヌル酸、２，６−ジ−tert−ブチルフェノール及びホルムアルデヒド類を、触媒としてトリエチルアミンを使用し、常圧下で、溶媒中で加熱反応させることにより得られる。
Hereinafter, the present invention will be described in detail.
The 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) thioisocyanuric acid of the present invention has a thiocyanuric acid, 2,6-di- It can be obtained by subjecting tert-butylphenol and formaldehyde to a heating reaction in a solvent under normal pressure using triethylamine as a catalyst.
前記の反応において、２，６−ジ−tert−ブチルフェノールの使用量は、チオシアヌル酸に対して、３〜１０倍モル、好ましくは３〜５倍モルである。 In the above reaction, the amount of 2,6-di-tert-butylphenol used is 3 to 10 times mol, preferably 3 to 5 times mol, of thiocyanuric acid.
本発明に使用し得るホルムアルデヒド類としては、ホルムアルデヒドを含有するか、または放出するものであればよく、ホルムアルデヒド液（ホルマリン）、パラホルムアルデヒド等が好適に使用される。パラホルムアルデヒドを使用する場合には、溶媒中に溶解させるため、必要に応じて水を併用することができる。
ホルムアルデヒド類の使用量は、ホルムアルデヒドとして、チオシアヌル酸に対して、３〜１０倍モル、好ましくは３〜５倍モルである。
As the formaldehydes that can be used in the present invention, any formaldehyde can be used as long as it contains or releases formaldehyde, and formaldehyde solution (formalin), paraformaldehyde, and the like are preferably used. When paraformaldehyde is used, water can be used in combination as necessary because it is dissolved in a solvent.
The amount of formaldehyde used is 3 to 10 times mol, preferably 3 to 5 times mol of thiocyanuric acid as formaldehyde.
トリエチルアミンの使用量は、チオシアヌル酸に対して、０．２〜１０倍モル、好ましくは０．５〜８倍モルである。 The usage-amount of a triethylamine is 0.2-10 times mole with respect to thiocyanuric acid, Preferably it is 0.5-8 times mole.
本発明に使用される溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン、アセトニトリル等が、また、メタノール、エタノール、イソプロピルアルコール、ブタノール等のアルコール類が挙げられるが、アセトニトリルやアルコール類が沸点が低く溶媒回収操作が容易であるので好ましい。 Examples of the solvent used in the present invention include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile and the like, and methanol, ethanol, isopropyl alcohol, butanol and the like. Among them, acetonitrile and alcohols are preferable because of low boiling point and easy solvent recovery operation.
反応温度は、６０℃以上であれば構わないが、温度制御の容易な還流温度が好ましい。反応時間は、１〜１０時間が好ましい。 The reaction temperature may be 60 ° C. or higher, but a reflux temperature with easy temperature control is preferred. The reaction time is preferably 1 to 10 hours.
加熱終了後、析出物を濾取し、溶媒で洗浄して１，３，５−トリス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)チオイソシアヌル酸を結晶として得ることができる。得られた結晶は、必要により再結晶法により精製することができる。 After heating, the precipitate is collected by filtration and washed with a solvent to obtain 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) thioisocyanuric acid as crystals. The obtained crystal can be purified by a recrystallization method if necessary.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されるものではない。
なお、実施例で使用した主原料は次のとおりである。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The main raw materials used in the examples are as follows.
［原料］
・チオシアヌル酸（東京化成工業社製、試薬）
・２，６−ジ−tert−ブチルフェノール（和光純薬工業社製、試薬）
・パラホルムアルデヒド（三菱瓦斯化学社製、純度９２％）
・アセトニトリル（和光純薬工業社製、試薬）
・トリエチルアミン（和光純薬工業社製、試薬）
[material]
・ Thiocyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)
・ 2,6-Di-tert-butylphenol (Wako Pure Chemical Industries, Reagent)
・ Paraformaldehyde (Mitsubishi Gas Chemical Company, purity 92%)
・ Acetonitrile (Wako Pure Chemical Industries, Reagent)
・ Triethylamine (Wako Pure Chemical Industries, Reagent)
〔実施例１〕
＜１，３，５−トリス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)チオイソシアヌル酸の合成＞
チオシアヌル酸４．４３ｇ（０．０２５ｍｏｌ）、２，６−ジ−tert−ブチルフェノール１５．７９ｇ（０．０７７ｍｏｌ）、パラホルムアルデヒド３．１８ｇ（ホルムアルデヒドとして０．０９８ｍｏｌ）及び水８．８６ｇを４４．３０ｇのアセトニトリルに入れ、次いでトリエチルアミン１５．２０ｇ（０．１５０ｍｏｌ）を加えて撹拌しながら４時間加熱還流を行った。反応終了後、反応混合物を室温まで冷却して析出物を濾取し、アセトニトリル１５．０ｇで洗浄した後、乾燥して白色粉末状の結晶１６．８５ｇ（０．０２０ｍｏｌ）を得た（収率８１．０％）。
[Example 1]
<Synthesis of 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) thioisocyanuric acid>
44.30 g of 4.43 g (0.025 mol) of thiocyanuric acid, 15.79 g (0.077 mol) of 2,6-di-tert-butylphenol, 3.18 g of paraformaldehyde (0.098 mol as formaldehyde) and 8.86 g of water Then, 15.20 g (0.150 mol) of triethylamine was added, and the mixture was heated to reflux with stirring for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitate was collected by filtration, washed with 15.0 g of acetonitrile, and then dried to obtain 16.85 g (0.020 mol) of white powdery crystals (yield) 81.0%).
得られた結晶の融点、純度、ＮＭＲ及びマススペクトルデータは、以下のとおりであった。
・融点：139-142℃
・純度：96.2％（高速液体クロマトグラフィーを使用して測定）
・NMR(CDCl3)：δ1.42(s,54H)，4.30(s,6H)，5.15(s,3H)，7.18(s,6H)
・MS(FAB+)m/z(%)：832(M+)
これらのスペクトルデータから、得られた結晶は、化３で示される１，３，５−トリス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)チオイソシアヌル酸であるものと同定した。
The melting point, purity, NMR and mass spectral data of the obtained crystal were as follows.
Melting point: 139-142 ° C
・ Purity: 96.2% (measured using high performance liquid chromatography)
NMR (CDCl 3 ): δ1.42 (s, 54H), 4.30 (s, 6H), 5.15 (s, 3H), 7.18 (s, 6H)
MS (FAB +) m / z (%): 832 (M +)
From these spectral data, the obtained crystal was identified as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) thioisocyanuric acid represented by Chemical Formula 3.
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