JPS6139939B2 - - Google Patents
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- Publication number
- JPS6139939B2 JPS6139939B2 JP52127554A JP12755477A JPS6139939B2 JP S6139939 B2 JPS6139939 B2 JP S6139939B2 JP 52127554 A JP52127554 A JP 52127554A JP 12755477 A JP12755477 A JP 12755477A JP S6139939 B2 JPS6139939 B2 JP S6139939B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- diamine
- general formula
- fatty acid
- 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.)
- Expired
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、ジアミンと高級脂肪酸とを反応させ
て高品質のイミダゾリン化合物を製造する方法に
関するものである。
両性活性剤は皮膚や毛髪に対して、比較的刺激
性が少なく、髪に柔軟性を与えると同時に優れた
洗浄力・起泡力を有しており、また、他のアニオ
ン活性剤やカチオン活性剤とも共存させうること
から、近年、シヤンプー、リンス、洗顔液などの
香粧品、化粧品あるいは台所用洗剤に使用される
ことが多くなつてきている。
両性活性剤の１種であるイミダゾリン型両性活
性剤の中間原料であるイミダゾリン化合物に対し
ては、上記の観点から高品質のものが要求され、
特に(1)色調(2)臭気(3)末反応物含有量(4)ジアマイド
などの副生物の含有量などの点で品質を総合的に
満足するものが要望されている。
高級脂肪酸とジアミンとを反応させてイミダゾ
リン化合物を合成する反応は縮合反応であり、脱
水が重要な工程であり、従来法としては共沸溶媒
法と無溶媒法がある。共沸溶媒法はキシロール等
の水と共沸する有機溶媒中で反応を行うものであ
り、無溶媒法と比較して反応温度が低くてすむた
め、色調の良好なものが得られ易いが、反応終了
後、溶媒を完全に除去することがむずかしく、溶
媒臭がいつまでも残るという欠点がある。このた
め、無溶媒法によつて、高品質のイミダゾリン化
合物を製造することが試みられてきた。
イミダゾリン化反応は、次式に従がつて進行す
ると考えられる。
この際(1)の反応で生成した酸アミドが脂肪酸と
反応して、次式に示すように、ジアマイドを副生
することがある。
（上記(1)〜(3)式においてＲは炭素数８〜20のアル
キル基又はアルケニル基を示し、Ｘは炭素原子数
２〜４のアルキロール基を示す）
このジアマイドは、それ自体有効成分として働か
ず、また、水に対する溶解性が低いため、ジアマ
イドを多く含むイミダゾリン化合物を両性化した
水溶液あるいはそれを配合した香粧品、化粧品水
溶液は白濁を生じ、商品外観を著るしく損ねる恐
れがある。このジアマイドの副生を抑制するには
(1)脂肪酸に対してジアミンを過剰にすること(2)生
成した反応水をできるだけ迅速に系外に除去する
ことが考えられ、例えば特公昭49−36235号に
は、生成水を迅速に系外に除去するために、一部
ジアミンを含む生成水を連続的に除去しながら、
全反応期間にわたつて、ジアミンを一定過剰量存
在させる、ジアマイド含量の少ないイミダゾリン
化合物の製造法が開示されている。しかしなが
ら、この方法では、反応途中でジアミンが失われ
るため新たにジアミンを追加する必要があるが、
それには、留出物の計量、留出物中のジアミンの
分析及び新たなジアミンの追加を全反応期間を通
して連続的に行なう必要があり、操作が非常にめ
んどうであり、実際的ではない。
本発明者らは上記の従来法の欠点を克服し、比
較的簡単な操作で効率的に高品質のイミダゾリン
化合物を製造する方法を開発するため、鋭意研究
を重ねた結果、反応温度170〜210℃で反応圧力を
ジアミンの蒸気圧より一定圧だけ高く保ち、反応
を進めることによりその目的が達成されることを
見出し、本発明を完成するに至つた。
すなわち、本発明は、一般式
H2N−CH2CH2−NHX
（ここでＸは炭素原子数２〜４のアルキルロール
基を示す）
で表わされるジアミンと、一般式
RCOOH
（ここでＲは炭素原子数８以上のアルキル基又は
アルケニル基を示す）
で表わされる高級脂肪酸とを反応させて、一般式
（ここでＲ及びＸは前記と同じ意味を持つ）
で表わされるイミダゾリン化合物を製造するに当
り、前記反応を、反応温度170〜210℃において、
かつこの温度におけるジアミンの蒸気圧より約15
〜150mmHg高い反応圧力下で、実質的に反応によ
り生成する水のみからなる留出物を連続的に徐去
しながら反応させることを特徴とするイミダゾリ
ン化合物の製造方法を提供するものである。
本発明で用いられる前記ジアミンとしては例え
ば、H2NCH2CH2NHC2H4OH、
H2NCH2CH2NHC3H6OHなどを挙げることができ
る。
また前記の一般式で表わされる高級脂肪酸とし
ては、例えばカプリル酸、カプリン酸、ラウリン
酸、ミリスチン酸、パルミチン酸、ステアリン
酸、オレイン酸、ノナデカン酸、ヤシ脂肪酸、硬
化牛脂脂肪酸などを挙げることができる。
本発明方法において高品質のイミダゾリン化合
物を得るためには反応温度は170〜210℃の範囲が
好ましく、170℃以下ではイミダゾリン化反応の
反応速度が小さく、満足な品質を達成できない。
また210℃を越えると反応物の熱分解及び酸化が
起り、反応生成物の異臭の発生と色調の劣化を引
き起す。反応圧力は、その反応温度におけるジア
ミンの蒸気圧より15〜150mmHg高くした圧力が好
ましく、差圧が15mmHg以下ではジアミンが幾分
蒸発して、生成水とともにジアミンも除去されて
しまうので、脂肪酸とジアミンの初期のモル比を
維持できなくなり、満足な反応率を達成できな
い。一方差圧が150mmHg以上では水の蒸発速度が
抑制され、反応の進行が阻害され、満足な反応率
を達成できない。
本発明において前記ジアミンと前記高級脂肪酸
とのモル比は、通常１：１〜1.5であり１：1.03
〜１：1.3が好ましい。
本発明方法によれば、色調が良好で臭気が少な
く、かつ末反応物や副生ジアマイドの含有量が少
ないイミダゾリン化合物を比較的簡単な操作で、
連続的に製造することができる。
次に本発明を実施例に基づき、さらに詳細に説
明する。
実施例
温度計、かきまぜ機、圧力計、コンデンサーに
連結した蒸気排出管及び滴下ロールを備えた密閉
反応フラスコに、かきまぜながら200ｇのヤシ脂
肪酸（平均分子量200）と109.2ｇのアミノエチル
エタノールアミン（AEEA、分子量104）を仕込
み、圧力を下げて、所定の反応圧力に保つてから
加熱をはじめた。
フラスコ内の温度が130℃になり、反応が始ま
り、生成水の蒸気の留出が始まつたら、昇温速度
をゆるめて、反応温度を徐々に上げていき、所定
の反応温度まで到達させた。反応開始から所定時
間後にフラスコ内の圧力を下げ、残存AEEAを留
出させた後、冷却し、反応生成物（イミダゾリ
ン）の性状を分析した。
反応生成物の性状を反応条件と共に次表に示
す。
The present invention relates to a method for producing a high quality imidazoline compound by reacting a diamine with a higher fatty acid. Amphoteric surfactants are relatively less irritating to the skin and hair, give flexibility to the hair, and at the same time have excellent detergency and foaming power. In recent years, it has been increasingly used in cosmetics, cosmetics, and kitchen detergents, as it can coexist with agents. Imidazoline compounds, which are intermediate raw materials for imidazoline-type amphoteric active agents, which are a type of amphoteric active agents, are required to be of high quality from the above viewpoints.
In particular, there is a demand for a product that satisfies overall quality in terms of (1) color, (2) odor, (3) content of end-reactants, and (4) content of by-products such as diamide. The reaction of synthesizing an imidazoline compound by reacting a higher fatty acid with a diamine is a condensation reaction, in which dehydration is an important step, and conventional methods include an azeotropic solvent method and a solvent-free method. In the azeotropic solvent method, the reaction is carried out in an organic solvent that is azeotropic with water, such as xylene, and the reaction temperature is lower than in the solvent-free method, so it is easier to obtain products with good color tone. It has the disadvantage that it is difficult to completely remove the solvent after the reaction is completed, and the solvent odor remains forever. For this reason, attempts have been made to produce high quality imidazoline compounds by solvent-free methods. The imidazolination reaction is thought to proceed according to the following formula. At this time, the acid amide produced in the reaction (1) may react with the fatty acid to produce diamide as a by-product, as shown in the following formula. (In the above formulas (1) to (3), R represents an alkyl group or alkenyl group having 8 to 20 carbon atoms, and X represents an alkylol group having 2 to 4 carbon atoms.) This diamide itself is an active ingredient. Also, because it has low solubility in water, an amphoteric aqueous solution of an imidazoline compound containing a large amount of diamide, or an aqueous solution of cosmetics or cosmetics containing the same, may become cloudy, which may seriously impair the appearance of the product. . To suppress this diamide by-product
(1) Excess diamine relative to fatty acid (2) Removal of generated reaction water from the system as quickly as possible. For example, Japanese Patent Publication No. 49-36235 describes In order to remove it to the outside, while continuously removing generated water containing some diamine,
A process for producing imidazoline compounds with low diamide content is disclosed in which a constant excess of diamine is present over the entire reaction period. However, with this method, diamine is lost during the reaction, so it is necessary to add new diamine.
For this purpose, it is necessary to measure the distillate, analyze the diamine in the distillate, and add new diamine continuously throughout the entire reaction period, which is very cumbersome and impractical. The present inventors have conducted extensive research in order to overcome the drawbacks of the above-mentioned conventional methods and to develop a method for efficiently producing high-quality imidazoline compounds with relatively simple operations. The present inventors have discovered that the objective can be achieved by maintaining the reaction pressure at a certain level higher than the vapor pressure of the diamine and allowing the reaction to proceed at a temperature of 0.degree. C., leading to the completion of the present invention. That is, the present invention provides a diamine represented by the general formula H2N - CH2CH2 - NHX (wherein X represents an alkylol group having 2 to 4 carbon atoms) and a diamine represented by the general formula RCOOH (wherein R is (representing an alkyl group or alkenyl group having 8 or more carbon atoms) is reacted with a higher fatty acid represented by the general formula (Here, R and X have the same meanings as above.) In producing the imidazoline compound represented by:
And the vapor pressure of diamine at this temperature is about 15
The present invention provides a method for producing an imidazoline compound, which is characterized in that the reaction is carried out under a high reaction pressure of ~150 mmHg while continuously gradually removing a distillate consisting essentially of water produced by the reaction. Examples of the diamine used in the present invention include H 2 NCH 2 CH 2 NHC 2 H 4 OH,
Examples include H 2 NCH 2 CH 2 NHC 3 H 6 OH. Examples of higher fatty acids represented by the above general formula include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, nonadecanoic acid, coconut fatty acid, and hydrogenated beef tallow fatty acid. . In order to obtain a high quality imidazoline compound in the method of the present invention, the reaction temperature is preferably in the range of 170 to 210°C, and below 170°C, the reaction rate of the imidazolination reaction is slow and satisfactory quality cannot be achieved.
Moreover, when the temperature exceeds 210°C, thermal decomposition and oxidation of the reactants occur, causing the generation of an unpleasant odor and deterioration of the color tone of the reaction product. The reaction pressure is preferably 15 to 150 mmHg higher than the vapor pressure of the diamine at the reaction temperature.If the differential pressure is less than 15 mmHg, the diamine will evaporate to some extent and the diamine will be removed along with the produced water, so fatty acids and diamine It becomes impossible to maintain the initial molar ratio of , and a satisfactory reaction rate cannot be achieved. On the other hand, if the differential pressure is 150 mmHg or more, the evaporation rate of water is suppressed, the progress of the reaction is inhibited, and a satisfactory reaction rate cannot be achieved. In the present invention, the molar ratio of the diamine to the higher fatty acid is usually 1:1 to 1.5, and 1:1.03.
~1:1.3 is preferred. According to the method of the present invention, an imidazoline compound with good color tone, low odor, and low content of end reactants and by-product diamide can be produced by relatively simple operations.
Can be manufactured continuously. Next, the present invention will be explained in more detail based on examples. EXAMPLE In a closed reaction flask equipped with a thermometer, a stirrer, a pressure gauge, a steam outlet connected to a condenser, and a dropping roll, 200 g of coconut fatty acid (average molecular weight 200) and 109.2 g of aminoethylethanolamine (AEEA) were added with stirring. , molecular weight 104) was charged, the pressure was lowered, and heating was started after maintaining the predetermined reaction pressure. Once the temperature inside the flask reached 130°C, the reaction began, and the vapor of the produced water began to distill off, the temperature increase rate was slowed down and the reaction temperature was gradually raised until the predetermined reaction temperature was reached. . After a predetermined time from the start of the reaction, the pressure inside the flask was lowered to distill off the remaining AEEA, and then cooled and the properties of the reaction product (imidazoline) were analyzed. The properties of the reaction products are shown in the following table along with the reaction conditions.
【表】
上記の結果より明らかなように、実験No.1〜
３においては、生成物中副生ジアマイドの含有量
が多く、また酸価も高い。また、実験No.8〜11
は副生ジアマイドの量が多く、色調が劣り、異臭
がつく傾向がある。これに対し、実験No.4〜７
の生成物は臭気、色調、酸価及び副生ジアマイド
の含有量の点から総合的に見て品質が優れてい
る。
参考例
反応途中で失われたジアミンを遂一追加しなが
ら行う方法に従がつてイミダゾリンを合成した。
まず温度計、かきまぜ機、圧力計、コンデンサ
ーに連続した蒸気排出管及び滴下ロートを備えた
密閉反応フラスコにかきまぜながら200ｇのヤシ
脂肪酸（平均分子量200）と114.4ｇのアミノエタ
ノールアミン（AEEA、分子量104）を仕込み圧
力を50mmHgに保つた。フラスコを加熱して、フ
ラスコ内の温度が130℃になつて反応が始まり、
生成水の蒸気が留出をはじめたら、昇温速度をお
として反応温度を徐々に上げていき、180℃付近
にもつていく。AEEAは反応温度165℃付近から
留出をはじめるので反応開始から２時間、３時
間、４時間経過した時点で留出物を分析し、留出
物中のAEEA量を測定し、同量の新しいAEEAを
滴下ロートから測定時点から30分おくれて計３回
フラスコに補充した。
反応開始後５時間後、圧力を10mmHg以下に下
げて、残存AEEAを留出させた後冷却し、反応生
成物の性状を分析した。その結果は次の通りであ
る。[Table] As is clear from the above results, Experiment No. 1~
In No. 3, the content of by-product diamide in the product was high, and the acid value was also high. Also, experiment No. 8-11
has a large amount of by-product diamide, has poor color tone, and tends to have a strange odor. In contrast, experiments No. 4 to 7
The product has excellent overall quality in terms of odor, color, acid value, and by-product diamide content. Reference Example An imidazoline was synthesized by following a method in which the diamine lost during the reaction was added once again. First, 200 g of coconut fatty acid (average molecular weight 200) and 114.4 g of aminoethanolamine (AEEA, molecular weight 104) were placed in a sealed reaction flask equipped with a thermometer, a stirrer, a pressure gauge, a steam outlet connected to a condenser, and a dropping funnel. ) was charged and the pressure was maintained at 50 mmHg. The flask is heated until the temperature inside the flask reaches 130°C and the reaction begins.
Once the vapor of the produced water begins to distill, the rate of heating is slowed down and the reaction temperature is gradually raised to around 180°C. AEEA begins to distill at a reaction temperature of around 165°C, so the distillate is analyzed 2, 3, and 4 hours after the start of the reaction, the amount of AEEA in the distillate is measured, and the same amount of new AEEA was replenished into the flask from the dropping funnel a total of three times at 30 minute intervals from the time of measurement. Five hours after the start of the reaction, the pressure was lowered to 10 mmHg or less to distill off the remaining AEEA, and then the mixture was cooled and the properties of the reaction product were analyzed. The results are as follows.
Claims (1)
を示す） で表わされるジアミンと一般式 RCOOH （ここでＲは炭素原子数８以上のアルキル基又は
アルケニル基を示す）で表わされる高級脂肪酸と
を反応させて、一般式 （ここでＲ及びＸは前記と同じ意味を持つ） で表わされるイミダゾリン化合物を製造するに当
り、前記反応を、反応温度170〜210℃、この温度
におけるジアミンの蒸気圧より約15〜150mmHg高
い反応圧力下で、反応生成水を連続的に留出除去
しながら行うことを特徴とするイミダゾリン化合
物の製法。[Claims] 1 A diamine represented by the general formula H 2 N-CH 2 CH 2 -NHX (wherein X represents an alkylol group having 2 to 4 carbon atoms) and a general formula RCOOH (where R is (representing an alkyl group or alkenyl group having 8 or more carbon atoms) is reacted with a higher fatty acid represented by the general formula (Here, R and X have the same meanings as above.) In producing the imidazoline compound represented by A method for producing an imidazoline compound, which is carried out under pressure while continuously distilling and removing reaction product water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12755477A JPS5461176A (en) | 1977-10-26 | 1977-10-26 | Preparation of imidazoline compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12755477A JPS5461176A (en) | 1977-10-26 | 1977-10-26 | Preparation of imidazoline compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5461176A JPS5461176A (en) | 1979-05-17 |
| JPS6139939B2 true JPS6139939B2 (en) | 1986-09-06 |
Family
ID=14962874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12755477A Granted JPS5461176A (en) | 1977-10-26 | 1977-10-26 | Preparation of imidazoline compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5461176A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7319898B2 (en) * | 2019-11-28 | 2023-08-02 | 三洋化成工業株式会社 | Method for producing imidazoline compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2773068A (en) * | 1955-07-11 | 1956-12-04 | Hans S Mannheimer | Substitution derivatives of imidazoline alkanoic quaternary ammonium hydroxide and process of preparing same |
| JPS4936235A (en) * | 1972-08-02 | 1974-04-04 | ||
| NO782799L (en) * | 1977-08-18 | 1979-02-20 | Albright & Wilson | PROCEDURES FOR THE PREPARATION OF IMIDAZOLINES |
-
1977
- 1977-10-26 JP JP12755477A patent/JPS5461176A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5461176A (en) | 1979-05-17 |
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