JP3026894B2 - Method for producing granular β-crystal tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane - Google Patents
Method for producing granular β-crystal tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methaneInfo
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- JP3026894B2 JP3026894B2 JP4253795A JP25379592A JP3026894B2 JP 3026894 B2 JP3026894 B2 JP 3026894B2 JP 4253795 A JP4253795 A JP 4253795A JP 25379592 A JP25379592 A JP 25379592A JP 3026894 B2 JP3026894 B2 JP 3026894B2
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- Prior art keywords
- propionyloxymethyl
- hydroxyphenyl
- methane
- butyl
- crystal
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は下記構造式The present invention relates to the following structural formula
【化１】 によって示されるβ晶構造を有するテトラキス〔３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）
プロピオニルオキシメチル〕メタン〔以下、化合物
（Ｉ）という。〕の新規な製造方法に関する。Embedded image Tetrakis having a β crystal structure represented by
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxymethyl] methane [hereinafter referred to as compound (I). ] Of the present invention.
【０００２】[0002]
【従来の技術】上記の化合物（Ｉ）は特公昭６２−２５
８３４３号公報等により開示された化合物であり、ポリ
オレフィン等に対する優れた酸化防止剤として広く用い
られている。BACKGROUND OF THE INVENTION The above compound (I) is disclosed in JP-B-62-25.
No. 8343, which is a compound disclosed widely and used as an excellent antioxidant for polyolefins and the like.
【０００３】通常の晶出方法で得られる粒子は、粒子径
が小さく、一定の粒子径を有する結晶が得られない。従
って、得られる粒子は、かさ比重が小さい、流動性が悪
い、飛散しやすい等の欠点があり、これを使用するにあ
たっては作業能率を低下させ、また作業環境上も問題が
ある。[0003] Particles obtained by a usual crystallization method have a small particle size, and crystals having a constant particle size cannot be obtained. Therefore, the obtained particles have drawbacks such as low bulk specific gravity, poor fluidity, and easy scattering, and use of these particles lowers the working efficiency and has a problem in the working environment.
【０００４】特開昭６２−２５８３４３号公報には、下
記〔化２〕および〔化３〕により示される混合物Ａの共
存下、メタノールおよび水系から晶出させて独立粒子状
β晶結晶を得ているが、共存させる混合物Ａを別途に得
る必要があるため操作が複雑である。[0004] Japanese Patent Application Laid-Open No. 62-258343 discloses that an independent particulate β crystal is obtained by crystallization from a methanol and water system in the presence of a mixture A represented by the following [Chemical Formula 2] and [Chemical Formula 3]. However, the operation is complicated because it is necessary to separately obtain the coexisting mixture A.
【０００５】[0005]
【化２】 （式中、Ｒ1 はメチル、エチルを示す。）Embedded image (In the formula, R 1 represents methyl or ethyl.)
【０００６】[0006]
【化３】 Embedded image
【０００７】また、特開平２−４９７５２号公報には、
反応粗製物をメタノールおよび水系からβ晶結晶を得て
いるが、晶出により微粉状結晶が得られた場合、再度粒
子径の大きな結晶を得ることが困難などの点で、従来の
製造方法は満足のいくものではない。Further, Japanese Patent Application Laid-Open No. 2-49752 discloses that
The reaction crude product is obtained from β-crystals from methanol and water system.However, when fine powder crystals are obtained by crystallization, it is difficult to obtain crystals having a large particle diameter again. Not satisfactory.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、簡便な製造
方法により、かさ比重が大きく、飛散および破砕し難
い、作業性のよい顆粒状β晶結晶を提供することを目的
とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a granular β crystal having a large bulk specific gravity, which is difficult to be scattered and crushed, and which has good workability by a simple production method.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記した
従来の晶出方法の欠点を克服すべく鋭意研究の結果、化
合物（Ｉ）をメタノール等の低級アルカノールから晶出
するに当たり、トルエンなどの芳香族炭化水素、または
それら混合溶媒と水を共存させることにより製造された
顆粒状β晶結晶は、粒子径が大きく、流動性にすぐれ、
破砕し難く、作業性のよいことを見出すとともに、反応
粗製体についてだけでなく微粉状結晶についても顆粒状
β晶結晶を晶出させることができることから、このよう
な簡便かつ経済的な製造方法を確立し、本発明を完成す
るに至った。Means for Solving the Problems The present inventors have conducted intensive studies to overcome the above-mentioned drawbacks of the conventional crystallization method. As a result, the compound (I) was crystallized from a lower alkanol such as methanol. Granular β-crystals produced by coexisting aromatic hydrocarbons such as, or a mixed solvent thereof and water, have a large particle diameter and excellent fluidity,
It is difficult to crush and finds good workability, and it is possible to crystallize granular β crystals not only for the reaction crude body but also for fine powder crystals. Established and completed the present invention.
【００１０】すなわち、本発明はテトラキス〔３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）
プロピオニルオキシメチル〕メタンを低級アルカノール
を溶媒として用いて晶出して、顆粒状β晶テトラキス
〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェ
ニル）プロピオニルオキシメチル〕メタンを製造する方
法において、低級アルカノール量に対し、０．１〜１
０．０重量％の芳香族炭化水素およびその混合溶媒量に
対し、４．０〜１２．０重量％の水を共存させ、晶出時
にβ晶テトラキス〔３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオニルオキシメチル〕メ
タンを種晶として加えることを特徴とする方法に関す
る。以下、これを詳細に説明する。That is, the present invention relates to tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Method for producing granular β-crystal tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane by crystallizing propionyloxymethyl] methane using a lower alkanol as a solvent At 0.1 to 1 with respect to the amount of lower alkanol.
4.0-12.0% by weight of water is allowed to coexist with 0.0% by weight of an aromatic hydrocarbon and a mixed solvent thereof, and β-tetrakis [3- (3,5-di-t -Butyl-4
-Hydroxyphenyl) propionyloxymethyl] methane as seed crystals. Hereinafter, this will be described in detail.
【００１１】化合物（Ｉ）の反応粗製体または微粉状結
晶を低級アルカノールを溶媒として低級アルカノール量
に対し、０．１〜１０．０重量％の芳香族炭化水素を含
有し、その混合溶媒量も対して４．０〜１２．０重量％
の水を含有した溶媒中に注加して晶出を行うことにより
得られる。The crude reaction product or fine powdery crystal of compound (I) contains 0.1 to 10.0% by weight of an aromatic hydrocarbon with respect to the amount of lower alkanol using lower alkanol as a solvent. 4.0 to 12.0% by weight
By crystallization by pouring into a solvent containing water.
【００１２】ここで、低級アルカノールとは、例えばメ
タノール、エタノール、イソプロピルアルコール、およ
びそれら混合溶媒などがあげられ、芳香族炭化水素と
は、例えばトルエン、キシレン、ベンゼンなどがあげら
れる。Here, the lower alkanol includes, for example, methanol, ethanol, isopropyl alcohol, and a mixed solvent thereof, and the aromatic hydrocarbon includes, for example, toluene, xylene, benzene and the like.
【００１３】また、結晶化を円滑に進行させるために
は、種晶としてβ晶結晶を添加することができ、結晶を
安定化させるためには、反応粗製体あるいは微粉状結晶
に対し、４．０〜１３．０重量％の水を添加してもよ
い。さらに、収率の向上を図り、スラリーは５〜２０℃
に冷却したほうがよい。[0013] Further, in order to promote crystallization smoothly, β crystal can be added as a seed crystal, and in order to stabilize the crystal, it is necessary to add 4.beta. 0-13.0% by weight of water may be added. Further, to improve the yield, the slurry is 5 to 20 ° C.
It is better to cool down.
【００１４】化合物（Ｉ）の反応粗製体は、化合物
（Ｉ）の反応終了物から低沸分のトルエンを減圧濃縮
し、着色防止のために窒素ガスで置換しながら常圧に戻
して得ることができる。The crude reaction product of compound (I) is obtained by concentrating toluene having a low boiling point under reduced pressure from the reaction product of compound (I) under reduced pressure, and returning to normal pressure while replacing with nitrogen gas to prevent coloring. Can be.
【００１５】本発明の好ましい態様として、テトラキス
〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェ
ニル）プロピオニルオキシメチル〕メタンをメタノール
を溶媒として用いて晶出して、顆粒状β晶テトラキス
〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェ
ニル）プロピオニルオキシメチル〕メタンを製造する方
法において、メタノール量に対し、０．１〜１０．０重
量％のトルエンおよびその混合溶媒量に対し、６．０〜
１０．０重量％の水を共存させる方法が挙げられる。In a preferred embodiment of the present invention, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane is crystallized using methanol as a solvent to obtain a granular β crystal. In a process for producing tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 0.1 to 10.0% by weight of toluene and a mixture thereof based on the amount of methanol 6.0 to the amount of solvent
A method in which 10.0% by weight of water coexists is exemplified.
【００１６】[0016]
【実施例】以下、実施例を示し、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。The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
【００１７】実施例１ テトラキス〔３−（３，５−ジ−ｔ−ブチル−４−ヒド
ロキシフェニル）プロピオニルオキシメチル〕メタンの
反応終了物を８０℃に加熱して減圧度２０ｍｍＨｇで低
沸分のトルエンを留去した。トルエンが留去しなくなっ
たら、さらに高度真空ポンプで減圧度５ｍｍＨｇ以下で
トルエンを留去し、内温１４０℃まで加熱を続けた。濃
縮が終わったら、着色を防止するために窒素ガスで置換
しながら常圧に戻して反応粗製体を得た。この反応粗製
体１５０ｇを攪拌機、還流冷却器、滴下ロート、温度計
を装着した５００ｍｌの４口フラスコに入れ、１４０℃
にて加熱溶解した後、滴下ロートから３．５重量％のト
ルエンを含有したメタノール８４．９ｇを徐々に滴下し
た（このとき、還流が激しく起こらないように初めはゆ
っくり滴下した。還流がおだやかになったら早く滴下し
てもよい。）。滴下後は内温を６５℃に維持した。別に
前もって攪拌機、還流冷却器、滴下ロート、温度計を装
着した１０００ｍｌの４口フラスコに３．５重量％のト
ルエンを含有したメタノール１４６．４ｇと水１２．５
ｇを入れ２０±１℃に保ち、この中に先の５００ｍｌフ
ラスコの内容物を注加して、β種晶０．１ｇを添加して
４０±１℃にて攪拌を続けた。１時間後に水１０．４ｇ
を加え、さらに１時間後に水８．０ｇを加えた。１時間
経過後、ゆっくり温度を下げ、３時間で２０℃まで冷却
した。３．５重量％のトルエンを含有したメタノール９
２．１５ｇと水４．８５ｇの混合溶媒で２回洗浄後、乾
燥し、顆粒状β晶結晶１１９．９ｇ（収率８０％）を得
た。Example 1 A reaction product of tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane was heated to 80 ° C., and a low boiling point was obtained at a reduced pressure of 20 mmHg. The toluene was distilled off. When the toluene was no longer distilled off, the toluene was further distilled off at a reduced pressure of 5 mmHg or less with an advanced vacuum pump, and heating was continued to an internal temperature of 140 ° C. After the concentration was completed, the pressure was returned to normal pressure while replacing with nitrogen gas in order to prevent coloring, thereby obtaining a crude reaction product. 150 g of the crude reaction product was placed in a 500 ml four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.
After heating and dissolving in, 84.9 g of methanol containing 3.5% by weight of toluene was gradually dropped from the dropping funnel (at this time, the mixture was dropped slowly at first so that reflux did not occur vigorously. It may be dropped as soon as possible.) After the dropwise addition, the internal temperature was maintained at 65 ° C. Separately, in a 1000 ml four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 146.4 g of methanol containing 3.5% by weight of toluene and 12.5 g of water were added.
g, and kept at 20 ± 1 ° C., into which the content of the 500 ml flask was poured, 0.1 g of β seed crystal was added, and stirring was continued at 40 ± 1 ° C. 10.4 g of water after 1 hour
Was added, and after one hour, 8.0 g of water was added. After 1 hour, the temperature was slowly lowered and cooled to 20 ° C. in 3 hours. Methanol 9 containing 3.5% by weight of toluene
After washing twice with a mixed solvent of 2.15 g and 4.85 g of water, drying was performed to obtain 119.9 g (yield: 80%) of granular β crystal.
【００１８】実施例２ ２．０重量％のトルエンを含有したメタノールを使用し
て、実施例１と同様に行った。顆粒状β晶結晶１２０．
４ｇ（収率８０％）を得た。Example 2 The procedure of Example 1 was repeated using methanol containing 2.0% by weight of toluene. Granular β crystal 120.
4 g (80% yield) were obtained.
【００１９】実施例３ １．０重量％のトルエンを含有したメタノールを使用し
て、実施例１と同様に行った。顆粒状β晶結晶１２２．
８ｇ（収率８２％）を得た。Example 3 The procedure of Example 1 was repeated, except that methanol containing 1.0% by weight of toluene was used. Granular β crystal 122.
8 g (82% yield) were obtained.
【００２０】比較例１ 実施例１の方法において、トルエン未添加にて晶出を行
った結果、微粉状β晶結晶１２６．５ｇ（収率８４％）
を得た。Comparative Example 1 Crystallization was carried out in the same manner as in Example 1 without the addition of toluene. As a result, 126.5 g of fine β-crystals were obtained (yield: 84%).
I got
【００２１】結果を第１表に示す。粒子の大きさは、ふ
るいで分離した結果を示す。The results are shown in Table 1. The size of the particles indicates the result of separation by sieving.
【００２２】[0022]
【表１】 表 １ ─────────────────────────────────── 実施例１ 実施例２ 実施例３ 比較例１ ─────────────────────────────────── トルエン（重量％） ３．５ ２．０ １．０ ０．０ 水 （重量％） ７．９ ７．９ ７．９ ０．０ ─────────────────────────────────── 粒 1.0mm 以上 ３．１ ６．１ １．７ ０．１ 子 1.0-0.5mm ７４ ７０ ７０ １．２ 径 0.5-0.25mm １６ １４ １９ ７５ （％） 0.25mm以下 ５．８ １０ ９．２ ２４ ─────────────────────────────────── 純度（％） ９６．４ ９６．５ ９６．３ ９７．１ ───────────────────────────────────Table 1 ─────────────────────────────────── Example 1 Example 2 Example 3 Comparative Example 1 例 Toluene (% by weight) 3.5 2.0 1 0.0 0.0 Water (% by weight) 7.9 7.9 7.9 0.0粒 Grain 1.0 mm or more 3.1 6.1 1.7 0.1 Child 1.0-0.5 mm 74 70 70 1.2 Diameter 0.5-0.25 mm 16 14 19 75 (%) 0.25 mm or less 8.8 10 9.2 24 純度 Purity (%) 96.4 96 5.5 96.3 97.1
【００２３】第１表に示した通り、本発明により得られ
る化合物（Ｉ）の結晶は粒子径１．０〜０．５ｍｍの範
囲に７０〜８０％を有するβ晶結晶であり、粒子径の大
きい、飛散しにくい顆粒状β晶結晶であることが判明し
た。As shown in Table 1, the crystals of compound (I) obtained according to the present invention are β-crystals having a particle size of 1.0 to 0.5 mm and having a particle size of 70 to 80%, It was found to be a large, hard-to-scatter granular β crystal.
【００２４】さらに、３００回／１分間の振盪機により
１時間振盪し、結晶の粒子硬度測定を行った結果を第２
表に示す。Further, the particles were shaken with a shaker 300 times / minute for 1 hour, and the particle hardness of the crystals was measured.
It is shown in the table.
【００２５】[0025]
【表２】 表 ２ ─────────────────────────────────── 実施例１ 実施例２ 実施例３ 比較例１ ─────────────────────────────────── 粒 1.0mm 以上 ３．５ ６．０ １．６ ０．０ 子 1.0-0.5mm ７３ ７０ ７０ １．１ 径 0.5-0.25mm １７ １５ １９ ７５ （％） 0.25mm以下 ７ ９ １０ ２４ ───────────────────────────────────[Table 2] Table 2 Example 1 Example 2 Example 3 Comparative Example 1 粒 grain 1.0 mm or more 3.5 6.0 1. 6 0.0 Child 1.0-0.5mm 73 70 70 1.1 Diameter 0.5-0.25mm 17 15 1975 (%) 0.25mm or less ───────────────────
【００２６】第２表に示した通り、化合物（Ｉ）の結晶
は、振盪後においても同じ粒度分布を示すことから、粒
子径が大きく、かつ破砕されにくい顆粒状β晶結晶であ
ることが判明した。As shown in Table 2, the crystals of compound (I) showed the same particle size distribution even after shaking, and thus were found to be granular β-crystals having a large particle size and being hardly crushed. did.
【００２７】実施例４ テトラキス〔３−（３，５−ジ−ｔ−ブチル−４−ヒド
ロキシフェニル）プロピオニルオキシメチル〕メタンの
微粉状結晶１５０ｇを実施例１と同様の装置に入れ、１
４０℃にて加熱溶解し、滴下ロートから５．５重量％の
トルエンを含有したメタノール８４．９ｇを徐々に滴下
した。滴下後、内温を６５℃に維持し、別のフラスコに
５．５重量％のトルエンを含有したメタノール１４６．
４ｇと水１２．５ｇを入れ２０±１℃に保ち、この中に
先のフラスコの内容物を注加し、β種晶０．１ｇを加え
た。１時間後に水１０．４ｇを加え、さらに１時間後に
水８．０ｇを加えた。１時間経過後、ゆっくり温度を下
げ、３時間で２０℃まで冷却した。５．５重量％のトル
エンを含有したメタノール９２．１５ｇと水４．８５ｇ
の混合溶媒で２回洗浄後、乾燥し、顆粒状β晶結晶１４
４．４ｇ（収率９６％）を得た。Example 4 150 g of fine powder of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane was placed in the same apparatus as in Example 1, and
The mixture was dissolved by heating at 40 ° C., and 84.9 g of methanol containing 5.5% by weight of toluene was gradually dropped from the dropping funnel. After the dropwise addition, the internal temperature was maintained at 65 ° C., and methanol containing 5.5% by weight of toluene was added to another flask.
4 g and 12.5 g of water were added and maintained at 20 ± 1 ° C., and the content of the flask was poured into the flask, and 0.1 g of β seed crystal was added. One hour later, 10.4 g of water was added, and one hour later, 8.0 g of water was added. After 1 hour, the temperature was slowly lowered and cooled to 20 ° C. in 3 hours. 92.15 g of methanol containing 5.5% by weight of toluene and 4.85 g of water
After washing twice with a mixed solvent of
4.4 g (96% yield) were obtained.
【００２８】比較例２ 実施例４と同様の操作を１２．０重量％のトルエンを含
有したメタノールを使用して行い、微粉状β晶結晶１４
５．３ｇ（収率９７％）を得た。Comparative Example 2 The same operation as in Example 4 was carried out using methanol containing 12.0% by weight of toluene to obtain fine powdered β-crystals 14.
5.3 g (97% yield) were obtained.
【００２９】微粉状結晶の再晶出を行った結果を第３表
に示す。Table 3 shows the results of recrystallization of the fine powdery crystals.
【００３０】[0030]
【表３】 表 ３ ──────────────────────────────── 微粉結晶 実施例４ 比較例２ ──────────────────────────────── トルエン（重量％） ── ５．５ １２．０ 水 （重量％） ── ７．９ ７．９ ──────────────────────────────── 粒 1.0mm 以上 ０．３ ０．３ ０．４ 子 1.0-0.5mm ５．４ ７０ ０．７ 径 0.5-0.25mm ８８ ２１ ９１ （％） 0.25mm以下 ６．１ ８．２ ８．０ ────────────────────────────────[Table 3] Fine powder crystal Example 4 Comparative example 2 ──────────────────────────── Toluene (% by weight) ── 5.5 12.0 Water (% by weight) ── 7. 9 7.9 mm 1.0mm or more 0.3 0.3 0.4 1.0-0.5mm 5.4 70 0.7 Diameter 0.5-0.25mm 88 2191 (%) 0.25mm or less 6.1 8.2 8.0 mm ────────────────
【００３１】第３表に示した通り、本発明により得られ
る化合物（Ｉ）の結晶は粒子径１．０〜０．５ｍｍの範
囲に７０％を有するβ晶結晶であり、微粉状結晶の再晶
出から容易に顆粒状β晶結晶が得られ、また、トルエン
添加量については０．１〜１０．０重量％が好ましいと
判明した。As shown in Table 3, the crystal of compound (I) obtained by the present invention is a β crystal having a particle diameter of 1.0 to 0.5 mm and having 70% in the range of 1.0 to 0.5 mm. Crystallized β-crystals were easily obtained from the crystallization, and it was found that the amount of toluene added was preferably 0.1 to 10.0% by weight.
【００３２】[0032]
【発明の効果】本発明の晶出方法により得た顆粒状β晶
結晶は、３００回／１分間の振盪機にて１時間振盪して
も破砕せず、そのままの粒度を保持することから、乾
燥、輸送などの工程において取り扱いやすく、流動性が
よく、かさ密度の大きいなどの特徴を有し、化合物の取
扱いを容易にし、作業性および作業環境の向上を図るこ
とができるという点で非常に有用である。The granular β-crystal obtained by the crystallization method of the present invention does not break even after being shaken for 1 hour with a shaker for 300 times / 1 minute, and retains the particle size as it is. It is easy to handle in processes such as drying and transportation, has good fluidity, and has a large bulk density.It is very easy to handle compounds and can improve workability and work environment. Useful.
【００３３】また、本発明の晶出方法によれば、反応粗
製体からだけでなく、微粉状結晶からもトルエン−メタ
ノール−水の混合溶媒にて簡便に顆粒状β晶結晶を得る
ことができる点で非常に有用である。According to the crystallization method of the present invention, granular β-crystals can be easily obtained not only from a crude reaction product but also from fine powder crystals with a mixed solvent of toluene-methanol-water. Very useful in that respect.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−99444（ＪＰ，Ａ) 特開 昭56−139438（ＪＰ，Ａ) 特開 平３−11037（ＪＰ，Ａ) 特開 平３−11038（ＪＰ，Ａ) 特開 平３−284652（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 67/52 C07C 69/732 ＣＡＰＬＵＳ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＷＰＩＤＳ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-56-99444 (JP, A) JP-A-56-139438 (JP, A) JP-A-3-11037 (JP, A) 11038 (JP, A) JP-A-3-284652 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 67/52 C07C 69/732 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)
Claims (4)
チル−４−ヒドロキシフェニル）プロピオニルオキシメ
チル〕メタンを低級アルカノールを溶媒として用いて晶
出して、顆粒状β晶テトラキス〔３−（３，５−ジ−ｔ
−ブチル−４−ヒドロキシフェニル）プロピオニルオキ
シメチル〕メタンを製造する方法において、低級アルカ
ノール量に対し、０．１〜１０．０重量％の芳香族炭化
水素およびその混合溶媒量に対し、４．０〜１２．０重
量％の水を共存させ、晶出時にβ晶テトラキス〔３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）
プロピオニルオキシメチル〕メタンを種晶として加える
ことを特徴とする方法。The present invention relates to the production of granular β-crystal tetrakis [3- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane using a lower alkanol as a solvent. (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyloxymethyl] methane in the amount of 0.1 to 10.0% by weight with respect to the amount of lower alkanol and 4.0 with respect to the amount of a mixed solvent thereof. ~ 12.0% by weight of water was allowed to coexist, and β-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
[Propionyloxymethyl] methane as a seed crystal.
ール、イソプロピルアルコールおよびそれらの混合溶媒
から選ばれる請求項１記載の方法。2. The method according to claim 1, wherein the lower alkanol is selected from methanol, ethanol, isopropyl alcohol and a mixed solvent thereof.
ベンゼンから選ばれる請求項１記載の方法。3. The method of claim 1, wherein the aromatic hydrocarbon is toluene, xylene,
The method of claim 1 wherein the method is selected from benzene.
チル−４−ヒドロキシフェニル）プロピオニルオキシメ
チル〕メタンをメタノールを溶媒として用いて晶出し
て、顆粒状β晶テトラキス〔３−（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシフェニル）プロピオニルオキシメ
チル〕メタンを製造する方法において、メタノール量に
対し、０．１〜１０．０重量％のトルエンおよびその混
合溶媒量に対し、６．０〜１０．０重量％の水を共存さ
せ、晶出時にβ晶テトラキス〔３−（３，５−ジ−ｔ−
ブチル−４−ヒドロキシフェニル）プロピオニルオキシ
メチル〕メタンを種晶として加えることを特徴とする方
法。4. Crystallization of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane using methanol as a solvent, yields granular β-crystal tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, the amount of 0.1 to 10.0% by weight of toluene based on the amount of methanol and the amount of a mixed solvent thereof based on the amount of methanol 6.0 to 10.0% by weight of water is allowed to coexist, and β-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxymethyl] methane as seed crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4253795A JP3026894B2 (en) | 1992-08-28 | 1992-08-28 | Method for producing granular β-crystal tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4253795A JP3026894B2 (en) | 1992-08-28 | 1992-08-28 | Method for producing granular β-crystal tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0672960A JPH0672960A (en) | 1994-03-15 |
| JP3026894B2 true JP3026894B2 (en) | 2000-03-27 |
Family
ID=17256261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4253795A Expired - Fee Related JP3026894B2 (en) | 1992-08-28 | 1992-08-28 | Method for producing granular β-crystal tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3026894B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808193A (en) * | 1985-12-28 | 1989-02-28 | Hoechst Aktiengesellschaft | Process for dyeing hydroxy-containing fiber material with water-soluble dis-azo reactive dye compound |
| CN102701979B (en) * | 2012-07-05 | 2014-04-16 | 营口市风光化工有限公司 | Method for purifying antioxidant 1010 |
| JP6518512B2 (en) * | 2015-05-27 | 2019-05-22 | 上野製薬株式会社 | Purification method of 4-hydroxybenzoic acid long chain ester |
-
1992
- 1992-08-28 JP JP4253795A patent/JP3026894B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0672960A (en) | 1994-03-15 |
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