JPH05155868A - Production of tris(4-hydroxybenzyl)isocyanurate compound - Google Patents
Production of tris(4-hydroxybenzyl)isocyanurate compoundInfo
- Publication number
- JPH05155868A JPH05155868A JP4125590A JP12559092A JPH05155868A JP H05155868 A JPH05155868 A JP H05155868A JP 4125590 A JP4125590 A JP 4125590A JP 12559092 A JP12559092 A JP 12559092A JP H05155868 A JPH05155868 A JP H05155868A
- Authority
- JP
- Japan
- Prior art keywords
- purity
- tert
- hydroxybenzyl
- tris
- isocyanuric acid
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリオレフィン類の酸
化防止剤として広く使用されている、トリス（３，５−
ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソ
シアヌレートを含む一般式The present invention relates to tris (3,5-), which is widely used as an antioxidant for polyolefins.
General formula containing di-tert-butyl-4-hydroxybenzyl) isocyanurate
【化３】 （式中、Ｒ1 は水素またはアルキルを、Ｒ2 はアルキル
を示す。）により表わされるトリス（４−ヒドロキシベ
ンジル）イソシアヌレート化合物を高収率に製造するた
めの改良方法に関する。[Chemical 3] (In the formula, R 1 represents hydrogen or alkyl, and R 2 represents alkyl.) The present invention relates to an improved process for producing a tris (4-hydroxybenzyl) isocyanurate compound in high yield.
【０００２】[0002]
【従来の技術】従来のトリス（３，５−ジ−ｔｅｒｔ−
ブチル−４−ヒドロキシベンジル）イソシアヌレートの
製造方法としては、特公昭５３−２８４３８号公報が知
られている。これには常圧反応と加圧反応が記載されて
いるが、常圧反応は特に低収率でしかも目的物の純度も
低いという欠点があった。BACKGROUND OF THE INVENTION Conventional tris (3,5-di-tert-
As a method for producing butyl-4-hydroxybenzyl) isocyanurate, JP-B-53-28438 is known. Although the atmospheric pressure reaction and the pressure reaction are described therein, the atmospheric pressure reaction has a drawback that the yield is particularly low and the purity of the target product is also low.
【０００３】[0003]
【発明が解決しようとする課題】上記した従来方法で好
適な触媒として使われているヘキサメチレンテトラミン
の場合、反応温度を１１０℃以上に上げる必要があるた
めにＮ，Ｎ−ジメチルホルムアミド、ジメチルスルホキ
シド、Ｎ−メチルピロリドン等の高沸点溶媒を使用して
いるが、目的物の収率や純度が低いばかりでなく、使用
する溶媒の沸点が高いため、溶媒の回収操作や目的物の
乾燥操作に不利がある。一方、前記溶媒に比べ、沸点の
低いアセトニトリル溶媒を使用する例が開示されている
が、沸点が低すぎるため所望の反応温度である１１０℃
を確保するために、圧力容器を用い加圧反応を行なって
いる。しかしながら、これも工業的方法としては有利な
方法とはいえず、アセトニトリル溶媒による常圧低温度
反応が要望されていた。本発明は回収が容易なアセトニ
トリルまたはアルコール類を溶媒として用いて、反応を
行い〔化３〕の化合物を高収率、高品質で得ることを目
的としている。In the case of hexamethylenetetramine, which is used as a suitable catalyst in the above-mentioned conventional method, it is necessary to raise the reaction temperature to 110 ° C. or higher, so that N, N-dimethylformamide and dimethylsulfoxide are required. , N-methylpyrrolidone and other high boiling point solvents are used, but not only the yield and purity of the target product are low, but also the boiling point of the solvent used is high, so it is suitable for solvent recovery and target product drying operations. There is a disadvantage. On the other hand, although an example of using an acetonitrile solvent having a lower boiling point than that of the above-mentioned solvent is disclosed, the boiling point is too low, which is a desired reaction temperature of 110 ° C.
In order to ensure the above, pressure reaction is performed using a pressure vessel. However, this is also not an advantageous method as an industrial method, and there has been a demand for a reaction under normal pressure and low temperature with an acetonitrile solvent. An object of the present invention is to obtain a compound of [Chemical Formula 3] in a high yield and a high quality by carrying out a reaction by using acetonitrile or an alcohol which is easily recovered as a solvent.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成するため
に、本発明者らは、一般式In order to achieve the above object, the inventors of the present invention have
【化４】 （式中、Ｒ1 ，Ｒ2 は前記と同義である。）により表わ
される化合物、イソシアヌル酸およびホルムアルデヒド
類との反応で、溶媒にアセトニトリルまたはアルコール
類を用いて、溶媒の沸点以下の反応温度で反応が完結で
きる各種触媒について鋭意検討を重ねた結果、塩基性触
媒の内、トリエチルアミン、ピぺリジンまたはジ−ｎ−
ブチルアミンを単独または併用使用することにより、再
結晶等の特別な精製操作を加えることなく、高純度、高
収率で〔化３〕の化合物が得られることを見いだし、本
発明を完成するに至った。[Chemical 4] (In the formula, R 1 and R 2 have the same meanings as described above.) In the reaction with the compound, isocyanuric acid and formaldehyde, acetonitrile or alcohol is used as a solvent at a reaction temperature not higher than the boiling point of the solvent. As a result of extensive studies on various catalysts capable of completing the reaction, among basic catalysts, triethylamine, piperidine or di-n-
It was found that by using butylamine alone or in combination, the compound of [Chemical Formula 3] can be obtained in high purity and high yield without adding a special purification operation such as recrystallization, and the present invention was completed. It was
【０００５】すなわち、本発明は〔化４〕の化合物、イ
ソシアヌル酸およびホルムアルデヒド類を塩基性触媒の
存在下、アセトニトリルまたはアルコール類を溶媒とし
て用い、反応させることを特徴とする〔化３〕の化合物
の製造法に関する。本明細書において、アルキルとは炭
素数１〜９個のアルキルを意味し、メチル、エチル、プ
ロピル、イソプロピル、ブチル、イソブチル、第３級ブ
チル、ペンチル、ネオペンチル、ヘキシル、オクチル、
２−エチルヘキシル、１，１，３，３−テトラメチルブ
チル、第３級ノニルなどがあげられる。溶媒として使用
されるアルコール類としては炭素数１〜４個のアルコー
ルが好ましく、メタノール、エタノール、イソプロピル
アルコールが例示される。本発明方法においては、アル
コール類を溶媒として用いる方が安価であり、回収もよ
り容易であることから、工業的に価値がある。ホルムア
ルデヒド類としては、ホルムアルデヒドを放出する化合
物であり、ホルマリン、パラホルムアルデヒドなどがあ
げられる。溶媒にアセトニトリルを使用する場合、塩基
性触媒であるピぺリジンおよびジ−ｎ−ブチルアミン
は、イソシアヌル酸１モルあたり３〜１５モル％、好ま
しくは５〜１０モル％使用する。触媒にトリエチルアミ
ンを用いる場合は、イソシアヌル酸１モルあたり２０〜
２００モル％、好ましくは５０〜１００モル％使用す
る。また、相乗効果による触媒活性を高める目的でピぺ
リジンまたはジ−ｎ−ブチルアミンとトリエチルアミン
を併用して用いることもできる。その場合は、イソシア
ヌル酸１モルあたりトリエチルアミン２０〜２００モル
％とピぺリジン０．５〜３モル％またはジ−ｎ−ブチル
アミン０．３〜２モル％、好ましくはトリエチルアミン
５０〜１００モル％とピぺリジン１〜２モル％またはジ
−ｎ−ブチルアミン０．５〜１モル％使用する。溶媒と
してアルコール類を用いる場合には、塩基性触媒として
はジ−ｎ−ブチルアミン単独、またはトリエチルアミン
との併用が好ましい。ジ−ｎ−ブチルアミンを用いる場
合には、イソシアヌル酸１モルあたり１０〜１００モル
％、好ましくは２０〜５０モル％がよい。また、相乗効
果による触媒活性を高める目的でジ−ｎ−ブチルアミン
とトリエチルアミンを併用して用いる場合は、イソシア
ヌル酸１モルあたりトリエチルアミン２０〜２００モル
％とジ−ｎ−ブチルアミン１〜２０モル％、好ましくは
トリエチルアミン５０〜１００モル％とジ−ｎ−ブチル
アミン２〜１０モル％がよい。反応は加圧下でも行われ
るが、常圧下の方が工業的である。反応温度は６０〜８
３℃、望ましくは溶媒の還流温度である。反応時間は触
媒の使用量、および反応温度により異なるが通常１〜１
５時間程度である。溶媒は、無水の必要はなく水が含ま
れていてもよい。本発明において、〔化４〕の化合物お
よびホルムアルデヒド類をイソシアヌル酸に対して１〜
１０モル％程度過剰に用いたときに最高収率を与えた。That is, the present invention is characterized by reacting the compound of [Chemical Formula 4], isocyanuric acid and formaldehydes in the presence of a basic catalyst using acetonitrile or alcohol as a solvent. Manufacturing method. In the present specification, alkyl means alkyl having 1 to 9 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, octyl,
2-ethylhexyl, 1,1,3,3-tetramethylbutyl, tertiary nonyl and the like can be mentioned. The alcohol used as the solvent is preferably an alcohol having 1 to 4 carbon atoms, and examples thereof include methanol, ethanol and isopropyl alcohol. In the method of the present invention, it is industrially valuable to use alcohols as a solvent because it is cheaper and easier to recover. Formaldehyde is a compound that releases formaldehyde, and examples thereof include formalin and paraformaldehyde. When acetonitrile is used as the solvent, the basic catalysts piperidine and di-n-butylamine are used in an amount of 3 to 15 mol%, preferably 5 to 10 mol% per 1 mol of isocyanuric acid. When triethylamine is used as the catalyst, it is 20-per mol of isocyanuric acid.
200 mol%, preferably 50 to 100 mol% is used. Further, piperidine or di-n-butylamine and triethylamine may be used in combination for the purpose of enhancing the catalytic activity due to a synergistic effect. In that case, 20 to 200 mol% of triethylamine and 0.5 to 3 mol% of piperidine or 0.3 to 2 mol% of di-n-butylamine, preferably 50 to 100 mol% of triethylamine per 1 mol of isocyanuric acid are used. Peridine 1-2 mol% or di-n-butylamine 0.5-1 mol% are used. When alcohols are used as the solvent, the basic catalyst is preferably di-n-butylamine alone or in combination with triethylamine. When di-n-butylamine is used, the amount is 10 to 100 mol%, preferably 20 to 50 mol% per 1 mol of isocyanuric acid. When di-n-butylamine and triethylamine are used in combination for the purpose of enhancing the catalytic activity due to a synergistic effect, 20-200 mol% of triethylamine and 1-20 mol% of di-n-butylamine are preferably used per 1 mol of isocyanuric acid, preferably Is preferably 50 to 100 mol% of triethylamine and 2 to 10 mol% of di-n-butylamine. The reaction is carried out under pressure, but it is more industrial under normal pressure. Reaction temperature is 60-8
3 ° C, preferably the reflux temperature of the solvent. The reaction time varies depending on the amount of the catalyst used and the reaction temperature, but is usually 1 to 1.
It takes about 5 hours. The solvent need not be anhydrous and may contain water. In the present invention, the compound of [Chemical formula 4] and formaldehydes are added in an amount of 1 to 1 with respect to isocyanuric acid.
The highest yield was obtained when used in excess of about 10 mol%.
【０００６】[0006]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.
【０００７】実施例１ ２，６−ジ−ｔｅｒｔ−ブチルフェノール１２９．９７
ｇ、イソシアヌル酸２５．８ｇ、パラホルムアルデヒド
（純度９２％）２０．５４ｇ、アセトニトリル２３２．
２ｇおよび水２５．８ｇをフラスコに入れ、ついでピぺ
リジン１．７ｇを加えて、攪拌しながら７時間加熱還流
を行った。ついで反応混合物を室温まで冷却したのち析
出物を濾取し、アセトニトリル水（水１０％）１００ｇ
で洗浄したのち、乾燥して１５１．４ｇのトリス（３，
５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）
イソシアヌレートを白色の結晶性粉末として得た（収率
９６．６％）。融点２１８．５〜２２０℃。高速液体ク
ロマトグラフィーによる純度９８．８％。Example 1 2,6-di-tert-butylphenol 129.97
g, isocyanuric acid 25.8 g, paraformaldehyde (purity 92%) 20.54 g, acetonitrile 232.
2 g and 25.8 g of water were put in a flask, 1.7 g of piperidine was then added, and the mixture was heated under reflux for 7 hours with stirring. Then, the reaction mixture was cooled to room temperature, the precipitate was collected by filtration, and 100 g of acetonitrile water (water 10%) was used.
After washing with, dried and 151.4 g of Tris (3,
5-di-tert-butyl-4-hydroxybenzyl)
Isocyanurate was obtained as a white crystalline powder (yield 96.6%). Melting point 218.5-220 [deg.] C. Purity 98.8% by high performance liquid chromatography.
【０００８】実施例２ ２，６−ジ−ｔｅｒｔ−ブチルフェノール６５ｇ、イソ
シアヌル酸１２．９ｇ、パラホルムアルデヒド（純度９
２％）１０．３ｇ、アセトニトリル１２０ｇおよび水１
０ｇをフラスコに入れ、ついでジ−ｎ−ブチルアミン１
ｇを加えて、攪拌しながら５時間加熱還流を行った。つ
いで反応混合物を実施例１と同様な処理を行なうことに
より、７５ｇのトリス（３，５−ジ−ｔｅｒｔ−ブチル
−４−ヒドロキシベンジル）イソシアヌレートを白色の
結晶粉末として得た（収率９５．６％）。融点２１８．
５〜２２０℃。高速液体クロマトグラフィーによる純度
９９．１％。Example 2 65 g of 2,6-di-tert-butylphenol, 12.9 g of isocyanuric acid, paraformaldehyde (purity 9
2%) 10.3 g, acetonitrile 120 g and water 1
0 g was placed in a flask, then di-n-butylamine 1
g was added, and the mixture was heated under reflux for 5 hours with stirring. Then, the reaction mixture was treated in the same manner as in Example 1 to obtain 75 g of tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate as a white crystalline powder (yield 95. 6%). Melting point 218.
5 to 220 ° C. Purity 99.1% by high performance liquid chromatography.
【０００９】実施例３ ２，６−ジ−ｔｅｒｔ−ブチルフェノール９７．５ｇ、
イソシアヌル酸１９．４ｇ、パラホルムアルデヒド（純
度９２％）１５．０ｇ、アセトニトリル１５６ｇおよび
水３０ｇをフラスコに入れ、ついでトリエチルアミン１
５ｇを加えて、攪拌しながら１１時間加熱還流を行っ
た。ついで反応混合物を実施例１と同様な処理を行っ
て、１１２．０ｇのトリス（３，５−ジ−ｔｅｒｔ−ブ
チル−４−ヒドロキシベンジル）イソシアヌレートを白
色の結晶性粉末として得た（収率９５．２％）。融点２
１８〜２２０℃。高速液体クロマトグラフィーによる純
度９９．４％。Example 3 97.5 g of 2,6-di-tert-butylphenol,
19.4 g of isocyanuric acid, 15.0 g of paraformaldehyde (purity 92%), 156 g of acetonitrile and 30 g of water were placed in a flask, and then triethylamine 1 was added.
5 g was added, and the mixture was heated under reflux for 11 hours with stirring. Then, the reaction mixture was treated in the same manner as in Example 1 to obtain 112.0 g of tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate as a white crystalline powder (yield. 95.2%). Melting point 2
18-220 ° C. Purity 99.4% by high performance liquid chromatography.
【００１０】実施例４ ２，６−ジ−ｔｅｒｔ−ブチルフェノール９７．４８
ｇ、イソシアヌル酸１９．３６ｇ、パラホルムアルデヒ
ド（純度９２％）１４．８２ｇ、アセトニトリル２００
ｇおよび水３０ｇをフラスコに入れ、ついでトリエチル
アミン１５ｇおよびピぺリジン０．１２５ｇを加えて、
攪拌しながら５．５時間加熱還流を行った。ついで反応
混合物を実施例１と同様な処理を行って、１１２．５ｇ
のトリス（３，５−ジ−ｔｅｒｔｒ−ブチル−４−ヒド
ロキシベンジル）イソシアヌレートを白色の結晶性粉末
として得た（収率９５．７％）。融点２１９〜２２０
℃。高速液体クロマトグラフィーによる純度９９．１
％。Example 4 2,6-di-tert-butylphenol 97.48
g, isocyanuric acid 19.36 g, paraformaldehyde (purity 92%) 14.82 g, acetonitrile 200
g and 30 g of water in a flask, and then 15 g of triethylamine and 0.125 g of piperidine are added,
The mixture was heated under reflux for 5.5 hours with stirring. Then, the reaction mixture was treated as in Example 1 to give 112.5 g.
Of tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate was obtained as a white crystalline powder (yield 95.7%). Melting point 219-220
° C. Purity 99.1 by high performance liquid chromatography
%.
【００１１】実施例５ ２，６−ジ−ｔｅｒｔ−ブチルフェノール１２９．９７
ｇ、イソシアヌル酸２５．８ｇ、パラホルムアルデヒド
（純度９２％）２０．５４ｇ、アセトニトリル２３２．
２ｇおよび水２５．８ｇをフラスコに入れ、ついでトリ
エチルアミン１０．１ｇおよびジ−ｎ−ブチルアミン
０．２６ｇを加えて、攪拌しながら３．５時間加熱還流
を行った。ついで反応混合物を実施例１と同様な処理を
行い、１５０．６ｇのトリス（３，５−ジ−ｔｅｒｔ−
ブチル−４−ヒドロキシベンジル）イソシアヌレートを
白色の結晶性粉末として得た（収率９６％）。融点２１
９〜２２０℃。高速液体クロマトグラフィーによる純度
９８．８％。Example 5 2,6-di-tert-butylphenol 129.97
g, isocyanuric acid 25.8 g, paraformaldehyde (purity 92%) 20.54 g, acetonitrile 232.
2 g and 25.8 g of water were put into a flask, then 10.1 g of triethylamine and 0.26 g of di-n-butylamine were added, and the mixture was heated under reflux for 3.5 hours with stirring. Then, the reaction mixture was treated in the same manner as in Example 1 to give 150.6 g of tris (3,5-di-tert-).
Butyl-4-hydroxybenzyl) isocyanurate was obtained as a white crystalline powder (yield 96%). Melting point 21
9-220 ° C. Purity 98.8% by high performance liquid chromatography.
【００１２】実施例６ ２，６−ジ−ｔｅｒｔ−ブチルフェノール１３０ｇ、イ
ソシアヌル酸２５．８ｇ、パラホルムアルデヒド（純度
９２％）２０．５ｇ、メタノール２３２．２ｇおよび水
２５．８ｇをフラスコに入れ、ついでジ−ｎ−ブチルア
ミン５．２ｇを加えて、攪拌しながら８時間加熱還流を
行った。ついで反応混合物を室温まで冷却したのち析出
物を濾取し、メタノール１５０ｇで洗浄したのち乾燥し
て、１４１．３ｇのトリス（３，５−ジ−ｔｅｒｔ−ブ
チル−４−ヒドロキシベンジル）イソシアヌレートを白
色の結晶性粉末として得た（収率９０．１％）。融点２
１６．５〜２１９℃。高速液体クロマトグラフィーによ
る純度９６．０％。Example 6 130 g of 2,6-di-tert-butylphenol, 25.8 g of isocyanuric acid, 20.5 g of paraformaldehyde (purity: 92%), 232.2 g of methanol and 25.8 g of water were placed in a flask, and then the mixture was added to the flask. 5.2 g of -n-butylamine was added, and the mixture was heated under reflux for 8 hours with stirring. Then, the reaction mixture was cooled to room temperature, the precipitate was collected by filtration, washed with 150 g of methanol and dried to obtain 141.3 g of tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate. Obtained as a white crystalline powder (yield 90.1%). Melting point 2
16.5-219 ° C. Purity 96.0% by high performance liquid chromatography.
【００１３】実施例７ ２，６−ジ−ｔｅｒｔ−ブチルフェノール１３０ｇ、イ
ソシアヌル酸２５．８ｇ、パラホルムアルデヒド（純度
９２％）２０．５ｇ、エタノール２３２．２ｇおよび水
２５．８ｇをフラスコに入れ、ついでジ−ｎ−ブチルア
ミン５．２ｇを加えて、攪拌しながら７時間加熱還流を
行った。ついで反応混合物を室温まで冷却したのち析出
物を濾取し、エタノール１５０ｇで洗浄したのち乾燥し
て、１４６．８ｇのトリス（３，５−ジ−ｔｅｒｔ−ブ
チル−４−ヒドロキシベンジル）イソシアヌレートを白
色の結晶性粉末として得た（収率９３．６％）。融点２
１８〜２１９．５℃。高速液体クロマトグラフィーによ
る純度９７．６％。Example 7 130 g of 2,6-di-tert-butylphenol, 25.8 g of isocyanuric acid, 20.5 g of paraformaldehyde (purity: 92%), 232.2 g of ethanol and 25.8 g of water were placed in a flask, and then the flask was charged with dihexane. 5.2 g of -n-butylamine was added, and the mixture was heated under reflux for 7 hours with stirring. Then, the reaction mixture was cooled to room temperature, the precipitate was collected by filtration, washed with 150 g of ethanol, and dried to obtain 146.8 g of tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate. Obtained as a white crystalline powder (yield 93.6%). Melting point 2
18-219.5 ° C. Purity 97.6% by high performance liquid chromatography.
【００１４】実施例８ ２，６−ジ−ｔｅｒｔ−ブチルフェノール１３０ｇ、イ
ソシアヌル酸２５．８ｇ、パラホルムアルデヒド（純度
９２％）２０．５ｇ、メタノール２３２．２ｇおよび水
２５．８ｇをフラスコに入れ、ついでトリエチルアミン
１０．１ｇおよびジ−ｎ−ブチルアミン１．３ｇを加え
て、攪拌しながら８時間加熱還流を行った。ついで反応
混合物を実施例６と同様の処理を行って、１４８．８ｇ
のトリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロ
キシベンジル）イソシアヌレートを白色の結晶性粉末と
して得た（収率９４．９％）。融点２１７．５〜２１
９．５℃。高速液体クロマトグラフィーによる純度９
７．０％。Example 8 130 g of 2,6-di-tert-butylphenol, 25.8 g of isocyanuric acid, 20.5 g of paraformaldehyde (purity 92%), 232.2 g of methanol and 25.8 g of water were placed in a flask, and then triethylamine was added. 10.1 g and 1.3 g of di-n-butylamine were added, and the mixture was heated under reflux for 8 hours with stirring. Then, the reaction mixture was treated as in Example 6 to give 148.8 g.
Of tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate was obtained as a white crystalline powder (yield 94.9%). Melting point 217.5-21
9.5 ° C. Purity by high performance liquid chromatography 9
7.0%.
【００１５】実施例９ ２，６−ジ−ｔｅｒｔ−ブチルフェノール１３０ｇ、イ
ソシアヌル酸２５．８ｇ、パラホルムアルデヒド（純度
９２％）２０．５ｇ、エタノール２３２．２ｇおよび水
２５．８ｇをフラスコに入れ、ついでトリエチルアミン
１０．１ｇおよびジ−ｎ−ブチルアミン０．６５ｇを加
えて、攪拌しながら８．５時間加熱還流を行った。つい
で反応混合物を実施例７と同様の処理を行って、１５
１．８ｇのトリス（３，５−ジ−ｔｅｒｔ−ブチル−４
−ヒドロキシベンジル）イソシアヌレートを白色の結晶
性粉末として得た（収率９６．８％）。融点２１８．５
〜２２０℃。高速液体クロマトグラフィーによる純度９
７．９％。Example 9 130 g of 2,6-di-tert-butylphenol, 25.8 g of isocyanuric acid, 20.5 g of paraformaldehyde (purity 92%), 232.2 g of ethanol and 25.8 g of water were placed in a flask, and then triethylamine was added. 10.1 g and di-n-butylamine 0.65 g were added, and the mixture was heated under reflux for 8.5 hours with stirring. The reaction mixture is then treated as in Example 7 to give 15
1.8 g Tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) isocyanurate was obtained as a white crystalline powder (yield 96.8%). Melting point 218.5
~ 220 ° C. Purity by high performance liquid chromatography 9
7.9%.
【００１６】実施例１０ ２，６−ジ−ｔｅｒｔ−ブチルフェノール１０２．８
ｇ、イソシアヌル酸１９．３６ｇ、パラホルムアルデヒ
ド（純度９２％）１６．０ｇ、イソプロピルアルコール
２００ｇおよび水１５ｇをフラスコに入れ、ついでトリ
エチルアミン２０ｇおよびジ−ｎ−ブチルアミン１．５
ｇを加えて、攪拌しながら３．５時間加熱還流を行っ
た。ついで反応混合物を室温まで冷却したのち析出物を
濾取し、イソプロピルアルコール１５０ｇで洗浄後、乾
燥して、１１５．７ｇのトリス（３，５−ジ−ｔｅｒｔ
−ブチル−４−ヒドロキシベンジル）イソシアヌレート
を白色の結晶性粉末として得た（収率９８．４％）。融
点２１９〜２２０．５℃。高速液体クロマトグラフィー
による純度９８．３％。Example 10 2,6-Di-tert-butylphenol 102.8
g, 19.36 g of isocyanuric acid, 16.0 g of paraformaldehyde (purity 92%), 200 g of isopropyl alcohol and 15 g of water were placed in a flask, and then 20 g of triethylamine and 1.5 of di-n-butylamine were added.
g was added, and the mixture was heated under reflux for 3.5 hours with stirring. Then, the reaction mixture was cooled to room temperature, the precipitate was collected by filtration, washed with 150 g of isopropyl alcohol, and dried to give 115.7 g of tris (3,5-di-tert).
-Butyl-4-hydroxybenzyl) isocyanurate was obtained as a white crystalline powder (yield 98.4%). Melting point 219-220.5 [deg.] C. Purity 98.3% by high performance liquid chromatography.
【００１７】実施例１１ ２−メチル−６−ｔｅｒｔ−ブチルフェノール１０４．
５ｇ、イソシアヌル酸２５．８ｇ、パラホルムアルデヒ
ド（純度９２％）２０．７４ｇ、イソプロピルアルコー
ル２７０ｇおよび水２０ｇをフラスコに入れ、ついでト
リエチルアミン２７ｇおよびジ−ｎ−ブチルアミン２．
０ｇを加えて、攪拌しながら１０時間加熱還流を行っ
た。ついで反応混合物からイソプロピルアルコールを留
去した残査にアセトニトリル２１０ｇと水３７ｇを加え
て攪拌した後、析出物を濾取し、アセトニトリル水（水
１０％）１５０ｍｌで洗浄後、乾燥して、１１６ｇのト
リス（３−メチル−５−ｔｅｒｔ−ブチル−４−ヒドロ
キシベンジル）イソシアヌレートを白色の結晶性粉末と
して得た（収率８８．１％）。融点１５７〜１５８℃。
高速液体クロマトグラフィーによる純度９９．１％。Example 11 2-Methyl-6-tert-butylphenol 104.
5 g, isocyanuric acid 25.8 g, paraformaldehyde (purity 92%) 20.74 g, isopropyl alcohol 270 g and water 20 g were placed in a flask, followed by triethylamine 27 g and di-n-butylamine 2.
0 g was added, and the mixture was heated under reflux for 10 hours with stirring. Then, 210 g of acetonitrile and 37 g of water were added to the residue obtained by distilling isopropyl alcohol from the reaction mixture, and the mixture was stirred, and then the precipitate was collected by filtration, washed with 150 ml of acetonitrile water (water 10%), and dried to give 116 g of Tris (3-methyl-5-tert-butyl-4-hydroxybenzyl) isocyanurate was obtained as a white crystalline powder (yield 88.1%). Melting point 157-158 [deg.] C.
Purity 99.1% by high performance liquid chromatography.
【００１８】実施例１２ ２−メチル−６−ｔｅｒｔ−ブチルフェノール１０４．
５ｇ、イソシアヌル酸２５．８ｇ、パラホルムアルデヒ
ド（純度９２％）２０．７４ｇ、アセトニトリル２５８
ｇおよび水３０ｇをフラスコに入れ、ついでトリエチル
アミン２７ｇおよびジ−ｎ−ブチルアミン２．０ｇを加
えて、攪拌しながら３時間加熱還流を行った。反応液に
５０％酢酸水３６ｇを加えて触媒を中和後、５５℃まで
冷却してこれにトリス（３−メチル−５−ｔｅｒｔ−ブ
チル−４−ヒドロキシベンジル）イソシアヌレート０．
２ｇを種晶として加えて１５℃まで冷却した。析出物を
濾取し、アセトニトリル水（水１５％）２００ｍｌで洗
浄後、乾燥して、１１２ｇのトリス（３−メチル−５−
ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシア
ヌレートを白色の結晶性粉末として得た（収率８５．１
％）。融点１５８〜１６０℃。高速液体クロマトグラフ
ィーによる純度９９．４％。Example 12 2-Methyl-6-tert-butylphenol 104.
5 g, isocyanuric acid 25.8 g, paraformaldehyde (purity 92%) 20.74 g, acetonitrile 258
g and 30 g of water were placed in a flask, 27 g of triethylamine and 2.0 g of di-n-butylamine were added, and the mixture was heated under reflux for 3 hours with stirring. After 36 g of 50% acetic acid water was added to the reaction solution to neutralize the catalyst, it was cooled to 55 ° C. and tris (3-methyl-5-tert-butyl-4-hydroxybenzyl) isocyanurate was added thereto.
2 g was added as a seed crystal and cooled to 15 ° C. The precipitate was collected by filtration, washed with 200 ml of acetonitrile water (15% water), and dried to give 112 g of tris (3-methyl-5-).
tert-Butyl-4-hydroxybenzyl) isocyanurate was obtained as a white crystalline powder (yield 85.1).
%). Melting point 158-160 [deg.] C. Purity 99.4% by high performance liquid chromatography.
【００１９】比較例１ 特公昭５３−２８４３８号公報の実施例１の方法に従っ
て追試試験を行った。窒素置換したフラスコにイソシア
ヌル酸３２．２５ｇ、２，６−ジ−ｔｅｒｔ−ブチル−
フェノール１６２．２ｇ、パラホルムアルデヒド（純度
７９．６１％）２８．３ｇおよび２００ｍｌのＮ，Ｎ−
ジメチルホルムアミドと２０ｍｌの水を仕込んだ。つい
で内容物を攪拌して１ｇのヘキサメチレンテトラミンを
加えて、攪拌しながら５時間、約１１２℃に加熱した。
ついで反応混合物を室温まで冷却し、メタノール１００
ｍｌを加えて析出物を濾取し、９０％メタノール水溶液
１００ｍｌで洗浄した後、乾燥して、１６８．９ｇのト
リス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ
ベンジル）イソシアヌレートを白色の結晶性粉末として
得た（収率８６．２％）。融点２１０〜２１６℃。高速
液体クロマトグラフィーによる純度９３．６％。Comparative Example 1 A follow-up test was conducted according to the method of Example 1 of Japanese Patent Publication No. 53-28438. 32.25 g of isocyanuric acid, 2,6-di-tert-butyl-in a flask purged with nitrogen.
162.2 g of phenol, 28.3 g of paraformaldehyde (purity 79.61%) and 200 ml of N, N-
Dimethylformamide and 20 ml of water were charged. The contents were then stirred and 1 g of hexamethylenetetramine was added and heated to 112 ° C for 5 hours with stirring.
The reaction mixture is then cooled to room temperature and methanol 100
ml was added, the precipitate was collected by filtration, washed with 100 ml of 90% aqueous methanol solution, and then dried to give 168.9 g of tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate as white. Was obtained as a crystalline powder of (yield 86.2%). Melting point 210-216 [deg.] C. Purity 93.6% by high performance liquid chromatography.
【００２０】比較例２ 比較例１の方法で、Ｎ，Ｎ−ジメチルホルムアミドのか
わりにアセトニトリルを用いて反応を行った。窒素置換
したフラスコにイソシアヌル酸１２．9 ｇ、２，６−ジ
−ｔｅｒｔ−ブチルフェノール６８．１ｇ、パラホルム
アルデヒド（純度７５．０％）１２．６ｇおよび１２０
ｇのアセトニトリルと１０ｇの水を仕込んだ。ついで内
容物を攪拌して１．７ｇのヘキサメチレンテトラミンを
加えて、攪拌しながら７時間、加熱還流を行った。この
反応では目的とするトリス（３，５−ジ−ｔｅｒｔ−ブ
チル−４−ヒドロキシベンジル）イソシアヌレートは得
られなかった。Comparative Example 2 The method of Comparative Example 1 was repeated except that acetonitrile was used instead of N, N-dimethylformamide. In a flask purged with nitrogen, 12.9 g of isocyanuric acid, 68.1 g of 2,6-di-tert-butylphenol, 12.6 g of paraformaldehyde (purity 75.0%) and 120
g acetonitrile and 10 g water were charged. Then, the content was stirred, 1.7 g of hexamethylenetetramine was added, and the mixture was heated under reflux for 7 hours with stirring. The target tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate was not obtained by this reaction.
【００２１】比較例３ ２，６−ジ−ｔｅｒｔ−ブチルフェノール１３０ｇ、イ
ソシアヌル酸２５．８ｇ、パラホルムアルデヒド（純度
９２％）２０．５ｇ、エタノール２３２．２ｇおよび水
２５．８ｇをフラスコに入れ、ついでヘキサメチレンテ
トラミン０．８ｇを加えて、攪拌しながら１０時間加熱
還流を行った。この反応でトリス（３，５−ジ−ｔｅｒ
ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレー
トは得られなかった。Comparative Example 3 130 g of 2,6-di-tert-butylphenol, 25.8 g of isocyanuric acid, 20.5 g of paraformaldehyde (purity 92%), 232.2 g of ethanol and 25.8 g of water were placed in a flask, and then hexa-hexene was added. 0.8 g of methylenetetramine was added, and the mixture was heated under reflux for 10 hours with stirring. In this reaction, tris (3,5-di-ter)
No t-butyl-4-hydroxybenzyl) isocyanurate was obtained.
【００２２】[0022]
【発明の効果】本発明方法により、トリス（４−ヒドロ
キシベンジル）イソシアヌレート化合物が高収率、高純
度に、しかも工業的に有利に製造される。INDUSTRIAL APPLICABILITY According to the method of the present invention, a tris (4-hydroxybenzyl) isocyanurate compound can be produced in high yield, high purity and industrially advantageously.
Claims (4)
を示す。）により表わされる化合物、イソシアヌル酸お
よびホルムアルデヒド類を塩基性触媒の存在下、アセト
ニトリルまたはアルコール類を溶媒として用いて反応さ
せることを特徴とする、一般式 【化２】 （式中、Ｒ1 ，Ｒ2 は前記と同義である。）により表わ
されるトリス（４−ヒドロキシベンジル）イソシアヌレ
ート化合物の製造法。1. A general formula: (Wherein R 1 represents hydrogen or alkyl, R 2 represents alkyl), isocyanuric acid and formaldehydes are reacted in the presence of a basic catalyst using acetonitrile or alcohols as a solvent. Which is characterized by the general formula: (In the formula, R 1 and R 2 have the same meanings as described above.) A process for producing a tris (4-hydroxybenzyl) isocyanurate compound.
ピぺリジンまたはジ−ｎ−ブチルアミンを使用すること
を特徴とする請求項１記載の方法。2. A basic catalyst, triethylamine,
Process according to claim 1, characterized in that piperidine or di-n-butylamine is used.
ピぺリジンまたはトリエチルアミンとジ−ｎ−ブチルア
ミンを併用して使用することを特徴とする請求項１記載
の方法。3. The method according to claim 1, wherein triethylamine and piperidine or triethylamine and di-n-butylamine are used in combination as the basic catalyst.
ノールまたはイソプロピルアルコールを使用することを
特徴とする請求項１記載の方法。4. The method according to claim 1, wherein methanol, ethanol or isopropyl alcohol is used as the alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4125590A JP2911296B2 (en) | 1991-04-19 | 1992-04-17 | Method for producing tris (4-hydroxybenzyl) isocyanurate compound |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11683991 | 1991-04-19 | ||
| JP20124691 | 1991-07-15 | ||
| JP3-201246 | 1991-07-15 | ||
| JP3-116839 | 1991-07-15 | ||
| JP4125590A JP2911296B2 (en) | 1991-04-19 | 1992-04-17 | Method for producing tris (4-hydroxybenzyl) isocyanurate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05155868A true JPH05155868A (en) | 1993-06-22 |
| JP2911296B2 JP2911296B2 (en) | 1999-06-23 |
Family
ID=27313241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4125590A Expired - Fee Related JP2911296B2 (en) | 1991-04-19 | 1992-04-17 | Method for producing tris (4-hydroxybenzyl) isocyanurate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2911296B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707122A (en) * | 2018-07-05 | 2018-10-26 | 营口风光新材料股份有限公司 | The method of one step high-pressure process biosynthesis block phenolic antioxidant 3114 |
-
1992
- 1992-04-17 JP JP4125590A patent/JP2911296B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707122A (en) * | 2018-07-05 | 2018-10-26 | 营口风光新材料股份有限公司 | The method of one step high-pressure process biosynthesis block phenolic antioxidant 3114 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2911296B2 (en) | 1999-06-23 |
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