JP2001097942A - Method for preparing monoglyceride sulfate - Google Patents

Method for preparing monoglyceride sulfate

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Publication number
JP2001097942A
JP2001097942A JP27383299A JP27383299A JP2001097942A JP 2001097942 A JP2001097942 A JP 2001097942A JP 27383299 A JP27383299 A JP 27383299A JP 27383299 A JP27383299 A JP 27383299A JP 2001097942 A JP2001097942 A JP 2001097942A
Authority
JP
Japan
Prior art keywords
compound
general formula
monoglyceride
represented
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.)
Pending
Application number
JP27383299A
Other languages
Japanese (ja)
Inventor
Takehiro Imanaka
健博 今中
Hiroshi Nagumo
博 南雲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP27383299A priority Critical patent/JP2001097942A/en
Publication of JP2001097942A publication Critical patent/JP2001097942A/en
Pending legal-status Critical Current

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a monoglyceride sulfate, scarcely forming by-products, such as inorganic salts including sodium sulfate, capable of conducting reaction without using solvents, having few restrictions on reactor, and therefore capable of preparing the product at a low cost. SOLUTION: This method for preparing the monoglyceride sulfate comprises reacting an acetal compound of monoglyceride or a ketal compound thereof expressed by general formula (1) (R1 is a residue formed by removing carboxy group from a 6-22C saturated or unsaturated fatty acid; R2 and R3 are each H, a 1-8C straight-chain alkyl, a 1-8C branched-chain alkyl or the like; X is H or-SO3M; and M is a cation) with a sulfating agent to form the monoglyceride sulfate compound of general formula (2).

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、洗浄基剤として有
用なモノグリセライドサルフェートの製造法に関する。
The present invention relates to a method for producing monoglyceride sulfate useful as a cleaning base.

【0002】[0002]

【従来の技術及び発明が解決しようとする課題】モノグ
リセライドサルフェートはその分子構造中に脂肪酸及び
グリセリン骨格を有し、低刺激性、かつ生分解性に優れ
た洗浄基剤として有用である。モノグリセライドサルフ
ェートの製造法として、グリセリンと3倍モルのクロル
スルホン酸からグリセリンのトリサルフェートを合成
し、その後硬化油脂を添加し、水/ブタノール抽出し、
最後に中和する方法(特開平1−104699)、油脂
と2倍モルのグリセリンを過剰の三酸化イオウで硫酸化
する方法(特開平6−503074、同6−50307
5)、ヤシ組成中純度モノグリセライドを三酸化イオウ
と反応させ、中和後過剰のNa2SO4をメンブラン膜で
濾過して除く方法(1996年 CESIO予稿集,A.BEHLER)等
が知られている。
2. Description of the Related Art Monoglyceride sulfate has a fatty acid and glycerin skeleton in its molecular structure, and is useful as a cleaning base having low irritation and excellent biodegradability. As a method for producing monoglyceride sulfate, trisulfate of glycerin is synthesized from glycerin and 3 times the molar amount of chlorosulfonic acid, and then a hardened fat is added, followed by extraction with water / butanol.
Finally, a method of neutralization (JP-A-1-104699) and a method of sulfating fats and oils and twice the amount of glycerin with excess sulfur trioxide (JP-A-6-503074 and JP-A-6-50307)
5), a method in which pure monoglyceride in coconut composition is reacted with sulfur trioxide, and after neutralization, excess Na 2 SO 4 is removed by filtration through a membrane membrane (1996, CESIO Proceedings, A. BEHLER). I have.

【0003】しかしながら、上記いずれの方法において
も、理論量より過剰の硫酸化剤を必要とし、多量の無機
塩が生成すること、酸性下におけるエステル交換のた
め、加水分解が起こりグリセリン、ジグリセライド、ト
リグリセライドの副生を伴うこと、溶媒抽出・メンブラ
ン濾過といった精製工程が不可欠となるとともに目的物
の収量が低いため製造コストの上昇を避けることができ
ない等の欠点を有していた。
However, any of the above methods requires an excess of the sulphating agent in excess of the stoichiometric amount, produces a large amount of inorganic salts, and undergoes hydrolysis due to transesterification under acidic conditions to cause glycerin, diglyceride, triglyceride. And the purification process such as solvent extraction and membrane filtration is indispensable, and the yield of the target product is low, so that the production cost cannot be avoided.

【0004】本発明の課題は、硫酸ナトリウム等の無機
塩の副生がほとんどなく、無溶媒でも生産が可能で、設
備上の制約も少ない、安価なモノグリセライドサルフェ
ートの製造法を提供することにある。
[0004] An object of the present invention is to provide an inexpensive method for producing monoglyceride sulfate, which can be produced without a solvent and has almost no by-products of inorganic salts such as sodium sulfate and can be produced with little restrictions on equipment. .

【0005】[0005]

【課題を解決するための手段】本発明は、一般式(1)According to the present invention, there is provided a compound represented by the general formula (1):

【0006】[0006]

【化5】 Embedded image

【0007】(式中、R1は炭素数6〜22の飽和又は不
飽和脂肪酸からカルボキシル基を除いた残基、R2及び
3は同一又は異なって、水素原子、炭素数1〜8の直
鎖又は分岐鎖のアルキル基もしくはR2とR3が連結して
環を形成する基を示す。)で表されるモノグリセライド
のアセタール又はケタール(以下化合物(1)という)
と硫酸化剤とを反応させ、更に必要により塩基成分で中
和する、一般式(2)で表されるモノグリセライドサル
フェートの製造法である。
(Wherein, R 1 is a residue obtained by removing a carboxyl group from a saturated or unsaturated fatty acid having 6 to 22 carbon atoms, R 2 and R 3 are the same or different and each represent a hydrogen atom, a C 1 to C 8 A straight chain or branched chain alkyl group or a group in which R 2 and R 3 are linked to form a ring; an acetal or ketal of a monoglyceride (hereinafter referred to as compound (1))
A monoglyceride sulfate represented by the general formula (2), wherein the monoglyceride sulfate is reacted with a sulfating agent and, if necessary, neutralized with a base component.

【0008】[0008]

【化6】 Embedded image

【0009】(式中、R1は前記と同じ意味を示し、X
は水素原子又は−SO3Mを示し、Mはアルカリ金属、
アルカリ土類金属、アンモニウム、モノ,ジ,トリもし
くはテトラアルキルアンモニウム、又はモノ,ジ,トリ
もしくはテトラアルカノールアンモニウム等の陽イオン
を示す。)
(Wherein, R 1 has the same meaning as described above;
Represents a hydrogen atom or -SO 3 M, M is an alkali metal,
A cation such as an alkaline earth metal, ammonium, mono, di, tri or tetraalkyl ammonium, or mono, di, tri or tetra alkanol ammonium. )

【0010】[0010]

【発明の実施の形態】本発明の製造原料となる化合物
(1)は、以下の2つの方法によって得ることができ
る。
BEST MODE FOR CARRYING OUT THE INVENTION The compound (1) as a raw material for production of the present invention can be obtained by the following two methods.

【0011】<方法1>グリセリンと一般式(3)<Method 1> Glycerin and general formula (3)

【0012】[0012]

【化7】 Embedded image

【0013】(式中、R2及びR3は前記の意味を示
す。)で表されるケトン類(以下化合物(3)という)
から一般式(4)
(Wherein R 2 and R 3 have the same meanings as described above) (hereinafter referred to as compound (3))
From general formula (4)

【0014】[0014]

【化8】 Embedded image

【0015】(式中、R2及びR3は前記の意味を示
す。)で表されるジオキソラン化合物(以下化合物
(4)という)を得た後、一般式(5) R1COOR4 (5) (式中、R1は前記の意味を示し、R4は水素原子、炭素
数1〜3のアルキル基又は油脂からR1COO基を除い
た残基を示す。)で表される脂肪酸、その低級アルキル
エステル又は油脂(以下化合物(5)という)でエステ
ル化する方法。
After obtaining a dioxolane compound (hereinafter referred to as compound (4)) represented by the formula (wherein R 2 and R 3 have the above-mentioned meanings), R 1 COOR 4 (5) (Wherein, R 1 represents the above-mentioned meaning, R 4 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a residue obtained by removing an R 1 COO group from fat or oil.) A method of esterifying with the lower alkyl ester or fat (hereinafter referred to as compound (5)).

【0016】<方法2>グリセリンと化合物(3)と化
合物(5)とを混合して反応させる方法。この場合にお
いて、混合は同時に行うことが好ましい。
<Method 2> A method in which glycerin, compound (3) and compound (5) are mixed and reacted. In this case, the mixing is preferably performed simultaneously.

【0017】ここで用いられる化合物(3)として、ア
セトン、メチルエチルケトン、メチルプロピルケトン、
メチルブチルケトン、ジエチルケトン、シクロヘキシル
ケトン等のケトン類、ホルムアルデヒド、アセトアルデ
ヒド、プロピオンアルデヒド、ブチルアルデヒド等のア
ルデヒド類が挙げられ、メチルエチルケトンが好まし
い。
As the compound (3) used herein, acetone, methyl ethyl ketone, methyl propyl ketone,
Examples thereof include ketones such as methyl butyl ketone, diethyl ketone, and cyclohexyl ketone, and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and butyl aldehyde, and methyl ethyl ketone is preferable.

【0018】また、化合物(5)として、炭素数6〜22
の脂肪酸、炭素数6〜22の脂肪酸残基を有する低級アル
キルエステル又は油脂が挙げられ、具体的には、カプロ
ン酸、カプリル酸、2−エチルヘキサン酸、ペラルゴン
酸、カプリン酸、ウンデシレン酸、ラウリン酸、ミリス
チン酸、パルミチン酸、ステアリン酸、アラキン酸、ベ
ヘン酸、パルミトオレイン酸、オレイン酸、リノール
酸、リノレン酸、イソパルミチン酸、イソステアリン酸
等の脂肪酸、或いはこれらの脂肪酸のメチル、エチル等
の低級アルキルエステル、ヤシ油、パーム油、パーム核
油、牛脂等の未硬化又は硬化油脂が挙げられ、ラウリン
酸、ヤシ油、パーム核油が好ましい。
The compound (5) may have 6 to 22 carbon atoms.
And lower alkyl esters or fats and oils having a fatty acid residue having 6 to 22 carbon atoms. Specific examples thereof include caproic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecylenic acid, and lauric acid. Fatty acids such as acid, myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, palmitooleic acid, oleic acid, linoleic acid, linolenic acid, isopalmitic acid, isostearic acid, or methyl and ethyl of these fatty acids And non-hardened or hardened oils such as coconut oil, palm oil, palm kernel oil and tallow, and lauric acid, coconut oil and palm kernel oil are preferred.

【0019】方法1において、グリセリンと化合物
(3)との反応は、例えば、0・5〜2モル%のp−トル
エンスルホン酸等の酸触媒の存在下、グリセリンに対し
て1.2〜1.5倍モルの化合物(3)、及び化合物(3)に
対してヘキサン、ヘプタン、トルエン等の炭化水素系溶
媒を0・3〜1・0重量倍使用し、Dien-Stark脱水管及び冷
却管を用いて、生成する水を該溶媒と共沸させながら系
外に放出させて、反応を行うことができる。
In the method 1, the reaction between glycerin and the compound (3) is carried out, for example, in the presence of 0.5 to 2 mol% of an acid catalyst such as p-toluenesulfonic acid, in an amount of 1.2 to 1.5 times the molar amount of glycerin. Compound (3), and a hydrocarbon solvent such as hexane, heptane, and toluene are used in an amount of 0.3 to 1.0 times by weight based on the compound (3), and a Dien-Stark dehydration tube and a cooling tube are used. The reaction can be carried out by releasing the generated water out of the system while azeotropically evaporating with the solvent.

【0020】また、化合物(4)と化合物(5)とのエ
ステル化反応は、仕込み原料全体に対し0.1〜2重量%
のナトリウムメチラート等の塩基触媒の存在下、好まし
くは80〜200℃、更に好ましくは120〜180℃で生成する
アルコール又は水を除去しながら行い、化合物(1)を
得る。ここで必要であれば触媒の中和、吸着処理、濾過
等の除去操作を行い、その後、減圧蒸留等の精製を行
う。
The esterification reaction between the compound (4) and the compound (5) is carried out in an amount of 0.1 to 2% by weight based on the whole raw materials.
The reaction is carried out in the presence of a base catalyst such as sodium methylate, preferably at 80 to 200 ° C, more preferably at 120 to 180 ° C, while removing alcohol or water, to obtain compound (1). If necessary, removal operations such as neutralization of the catalyst, adsorption treatment, and filtration are performed, and then purification such as distillation under reduced pressure is performed.

【0021】また、方法2は、一段階で化合物(1)を
得る方法である。この場合には、仕込み原料全体に対し
て0.1〜2重量%のパラトルエンスルホン酸等の酸触媒
存在下、好ましくは60〜200℃、更に好ましくは80〜120
℃で生成する水を除去しながらケタール又はアセタール
化反応とエステル化反応を同時に行う。ここで必要であ
れば触媒の中和、吸着処理、濾過等の除去操作を行い、
その後、減圧蒸留等の精製を行う。
The method 2 is a method for obtaining the compound (1) in one step. In this case, in the presence of an acid catalyst such as paratoluenesulfonic acid in an amount of 0.1 to 2% by weight based on the whole charged raw material, preferably 60 to 200 ° C, more preferably 80 to 120 ° C.
The ketal or acetalization reaction and the esterification reaction are simultaneously performed while removing the water generated at ° C. If necessary, neutralization of the catalyst, adsorption treatment, removal operations such as filtration, etc.,
Thereafter, purification such as distillation under reduced pressure is performed.

【0022】本発明において、化合物(1)と反応させ
る硫酸化剤として、硫酸、発煙硫酸、硫酸水素塩(アル
カリ金属塩、アルカリ土類金属塩、アンモニウム塩、モ
ノ,ジ,トリもしくはテトラアルキルアンモニウム塩
(総炭素数1〜32)、モノ,ジ,トリもしくはテトラア
ルカノールアンモニウム塩(総炭素数2〜32)等)等が
挙げられ、好ましくは、硫酸、発煙硫酸、硫酸水素カリ
ウム、硫酸水素アンモニウムである。硫酸化剤の量は、
中和物中の無機硫酸塩の生成を抑えるために、化合物
(1)に対し0.3〜3.0モル倍が好ましく、0.8〜1.0モル
倍が更に好ましい。
In the present invention, sulfuric acid, fuming sulfuric acid, hydrogen sulfate (alkali metal salt, alkaline earth metal salt, ammonium salt, mono-, di-, tri- or tetraalkylammonium) may be used as a sulfating agent to react with compound (1). Salts (total carbon number of 1 to 32), mono, di, tri or tetraalkanol ammonium salts (total carbon number of 2 to 32) and the like. Preferred are sulfuric acid, fuming sulfuric acid, potassium hydrogen sulfate and ammonium hydrogen sulfate. It is. The amount of sulfating agent is
In order to suppress the formation of the inorganic sulfate in the neutralized product, the amount is preferably 0.3 to 3.0 mol times, more preferably 0.8 to 1.0 mol times, relative to the compound (1).

【0023】本発明の硫酸化反応の反応温度は、温度が
低すぎると、特に無溶媒の場合、系内はぺースト状とな
り増粘をきたし、一方、高温ではエステル交換の併発に
より脂肪酸の遊離やジグリセライドやトリグリセライド
の副生が生じるので、−20〜110℃が好ましく、30〜90
℃が更に好ましい。また反応時間は、反応温度や溶媒に
より変化するが、好ましくは数時間、更に好ましくは1
〜10時間である。
If the reaction temperature of the sulfation reaction of the present invention is too low, especially in the absence of a solvent, the system becomes paste-like and thickens. On the other hand, at a high temperature, the liberation of fatty acids is caused by simultaneous transesterification. -20 to 110 ° C. is preferable, and 30 to 90 ° C. is preferable since by-products of diglyceride and triglyceride occur.
C is more preferred. The reaction time varies depending on the reaction temperature and the solvent, but is preferably several hours, more preferably 1 hour.
~ 10 hours.

【0024】硫酸化剤として硫酸水素塩を使用する場合
は生成物が固化するため溶媒を必要とする。溶媒は、ヘ
プタンやテトラヒドロフラン等の非極性溶媒からアセト
ニトリルやジメチルスルホキシド等の極性溶媒まで各種
溶媒を使用できる。硫酸又は発煙硫酸を使用した場合は
無溶媒でも生成物は液体であり、強いて溶媒を併用する
必要はない。
When hydrogen sulfate is used as the sulfating agent, a solvent is required because the product solidifies. Various solvents can be used as the solvent, from non-polar solvents such as heptane and tetrahydrofuran to polar solvents such as acetonitrile and dimethyl sulfoxide. When sulfuric acid or fuming sulfuric acid is used, the product is a liquid even without solvent, and it is not necessary to use a solvent together.

【0025】本発明の硫酸化反応では反応の進行ととも
にアルデヒド又はケトンが生成してくるので系内を減圧
にしてこれを留去すると、反応の平衡がずれ、未反応の
化合物(1)の量を低減できるので好ましい。減圧度
は、溶媒を用いた場合にはその沸点によるが、無溶媒の
場合には2.7〜6.7kPaが好ましい。
In the sulfation reaction of the present invention, aldehydes or ketones are generated with the progress of the reaction. If the system is depressurized and distilled off, the equilibrium of the reaction is shifted and the amount of the unreacted compound (1) is reduced. This is preferable because it can reduce The degree of pressure reduction depends on the boiling point when a solvent is used, but is preferably 2.7 to 6.7 kPa when no solvent is used.

【0026】更に中和を行う場合、用いる塩基成分とし
て、アルカリ金属もしくはアルカリ土類金属の水酸化
物、炭酸塩もしくはアルコキシドや、アンモニア、モ
ノ,ジ,トリアルキルアミンもしくはテトラアルキルア
ンモニウム塩(総炭素数1〜32)、又はモノ,ジ,トリ
アルカノールアミンもしくはテトラアルカノールアンモ
ニウム塩(総炭素数2〜32)等が挙げられるが、好まし
くはNaOH、KOH、Na2CO3、アンモニアであ
る。
In the case of further neutralization, as a base component to be used, an alkali metal or alkaline earth metal hydroxide, carbonate or alkoxide, ammonia, mono, di, trialkylamine or tetraalkylammonium salt (total carbon the number 1 to 32), or mono-, di-, tri-alkanolamine or tetra alkanolammonium salts (total carbon number 2 to 32) and others as mentioned, preferably NaOH, KOH, Na 2 CO 3 , ammonia.

【0027】中和は普通水溶液で行うが、反応物に塩基
成分の水溶液を添加した場合、中和初期に低pHのため
脂肪酸エステルとサルフェートの両方の加水分解が起こ
る。従って、塩基成分の水溶液に冷水で冷却しながら反
応物を添加することが好ましい。また、高濃度の塩基成
分水溶液への中和では、やはり加水分解を併発しやすい
ので、中和終了時固形分が30重量%以下になるように水
溶液の濃度を調整することが好ましい。
The neutralization is usually carried out with an aqueous solution, but when an aqueous solution of a base component is added to the reaction product, hydrolysis of both the fatty acid ester and the sulfate occurs due to a low pH in the early stage of the neutralization. Therefore, it is preferable to add the reactants to the aqueous solution of the base component while cooling with cold water. Further, in the neutralization to a high-concentration aqueous solution of the base component, hydrolysis is also likely to occur simultaneously. Therefore, it is preferable to adjust the concentration of the aqueous solution so that the solid content at the end of the neutralization is 30% by weight or less.

【0028】本発明の方法により得られたモノグリセラ
イドサルフェートはそのまま使用してもよいし、要すれ
ば、再結晶、電気透析、溶媒抽出等の方法により精製し
てもよい。
The monoglyceride sulfate obtained by the method of the present invention may be used as it is, or if necessary, may be purified by a method such as recrystallization, electrodialysis, or solvent extraction.

【0029】[0029]

【実施例】例中の%は特記しない限り重量%である。EXAMPLES In the examples,% is% by weight unless otherwise specified.

【0030】合成例1 グリセリン230.26g(2.5モル)、メチルエチルケトン27
0.43g(3.75モル)、ヘプタン109.65g及びパラトルエ
ンスルホン酸4.77gをフラスコに仕込み、400rpmで撹拌
しながら還流した。9時間後所定の脱水量に達したので
反応を終了した。これを5回繰り返して、反応終了物を
混合した。28%ナトリウムメチラート(メタノール溶
液)30.71gで触媒を中和したところ5%水溶液のpH
が9.8であった。これを40〜87℃、真空度40〜0.8kPaま
で上げて、ヘプタンとメチルエチルケトンを留去した
後、50〜85℃で0.67kPa蒸留を行い、1579.5gのグリセ
リンのメチルエチルケトンのケタールを得た(収率75.8
%、ガスクロマトグラフィー純度97.59%)。
Synthesis Example 1 230.26 g (2.5 mol) of glycerin, methyl ethyl ketone 27
0.43 g (3.75 mol), 109.65 g of heptane and 4.77 g of p-toluenesulfonic acid were charged into a flask and refluxed while stirring at 400 rpm. Nine hours later, the reaction was terminated because a predetermined amount of dehydration was reached. This was repeated five times, and the reaction finished product was mixed. The catalyst was neutralized with 30.71 g of 28% sodium methylate (methanol solution).
Was 9.8. The pressure was raised to 40 to 87 ° C. and the degree of vacuum to 40 to 0.8 kPa. After distilling off heptane and methyl ethyl ketone, distillation at 50 to 85 ° C. was performed at 0.67 kPa to obtain 1579.5 g of glycerin methyl ethyl ketone ketal. Rate 75.8
%, Gas chromatography purity 97.59%).

【0031】次にラウリン酸メチルエステル1071.75g
(5モル)、グリセリンのメチルエチルケトンのケター
ル1461.9g(10モル)及び28%ナトリウムメチラート
(メタノール溶液)50.67gをフラスコに仕込み、窒素
フロー下500rpmで撹拌しながら、180℃、3時間加熱反
応した。協和化学社製キヨワード600Sを35.47g添加
し、80℃で1時間吸着処理を行った。室温まで冷却後、
濾過して2178.0gの反応物を得た。これを176〜183℃、
0.08kPaで蒸留して1321.4gのC12モノグリセライドの
メチルエチルケトンのケタールを得た(収率80.5%、ガ
スクロマトグラフィー純度98.97%)。このもののケン
化価は168.1 KOHg/kgで理論値の170.8 KOHg/kgとよ
く一致した。
Next, 1071.75 g of lauric acid methyl ester
(5 moles), 1461.9 g (10 moles) of a glycerin methyl ethyl ketone ketal and 50.67 g of 28% sodium methylate (methanol solution) were charged into a flask, and heated at 180 ° C. for 3 hours while stirring at 500 rpm under a nitrogen flow. . 35.47 g of Kyoword 600S manufactured by Kyowa Chemical Industry Co., Ltd. was added, and an adsorption treatment was performed at 80 ° C. for 1 hour. After cooling to room temperature,
Filtration gave 2178.0 g of reaction. 176-183 ° C,
Distilled at 0.08kPa to give the C 12 methyl ethyl ketone ketal of monoglyceride of 1321.4g (80.5% yield, gas chromatographic purity 98.97%). Its saponification value was 168.1 KOHg / kg, which was in good agreement with the theoretical value of 170.8 KOHg / kg.

【0032】実施例1 合成例1のモノグリセライドのケタール32.85g(0.1モ
ル)、硫酸水素カリウム13.62g(0.1モル)及びジメチ
ルスルホキシド150gをフラスコに仕込み、50℃、6.7kP
aで9時間、70℃、6.7kPaで2.5時間反応させメチルエチ
ルケトンを系外に留去しながら硫酸化した。反応終了物
の高速液体クロマトグラフィーの組成はモノグリセライ
ド38.9%、モノグリセライドモノサルフェート54.5%及
び未反応モノグリセライドケタール2.2%であった。
Example 1 A flask was charged with 32.85 g (0.1 mol) of the monoglyceride ketal of Synthesis Example 1, 13.62 g (0.1 mol) of potassium hydrogen sulfate and 150 g of dimethyl sulfoxide.
The mixture was reacted for 9 hours at 70 ° C. and 6.7 kPa for 2.5 hours, and sulfated while distilling off methyl ethyl ketone out of the system. The high-performance liquid chromatography composition of the reaction product was 38.9% monoglyceride, 54.5% monoglyceride monosulfate, and 2.2% unreacted monoglyceride ketal.

【0033】これを48%KOH水溶液で完全に中和して
濾過後濃縮し、エタノール100gで再結晶させた。吸引
濾過後減圧乾燥して4.8gの結晶を得た。これを更に氷
冷下脱イオン水25gで再結晶させ、吸引濾過後減圧乾燥
して1.0gのモノグリセライドモノサルフェートを得た
(収率2.5%、高速液体クロマトグラフィー純度97.25
%)。赤外線吸収スペクトルでは1730cm-1に脂肪酸エス
テルの吸収、3400cm-1に水酸基の吸収が確認できた。ま
た、13C−NMRではグリセリン炭素の化学シフトは、
硫酸エステルのついたCH2は71.7ppm、CHは70.2pp
m、脂肪酸エステルのついたCH2は67.5ppmであり、特
開平6−306041号公報の10頁に記載のα−モノグ
リセライドモノサルフェートの13C−NMRのグリセリ
ン炭素の化学シフトとほぼ一致した。
This was completely neutralized with a 48% KOH aqueous solution, filtered, concentrated, and recrystallized with 100 g of ethanol. After suction filtration and drying under reduced pressure, 4.8 g of crystals were obtained. This was further recrystallized from deionized water (25 g) under ice-cooling, filtered by suction and dried under reduced pressure to obtain 1.0 g of monoglyceride monosulfate (yield 2.5%, high-performance liquid chromatography purity 97.25).
%). Infrared absorption absorption fatty acid esters to 1730 cm -1 in the spectrum, the absorption of hydroxyl groups was confirmed in 3400 cm -1. In 13 C-NMR, the chemical shift of glycerin carbon is
71.7 ppm for CH 2 with sulfate ester, 70.2 pp for CH
m, CH 2 equipped with a fatty acid ester is 67.5Ppm, almost consistent with α- monoglyceride 13 C-NMR chemical shifts of glycerol carbon in the monosulfate described in page 10 of JP-A 6-306041 JP.

【0034】実施例2 合成例1のモノグリセライドケタール32.85g(0.1モ
ル)、硫酸水素アンモニウム11.51g(0.1モル)及びジ
メチルスルホキシド150gをフラスコに仕込み、90℃、
6.7kPaで9.5時間反応させた。反応終了品の高速液体ク
ロマトグラフィーの組成を表1に示す。
Example 2 A flask was charged with 32.85 g (0.1 mol) of the monoglyceride ketal of Synthesis Example 1, 11.51 g (0.1 mol) of ammonium hydrogen sulfate and 150 g of dimethyl sulfoxide.
The reaction was performed at 6.7 kPa for 9.5 hours. Table 1 shows the composition of the reaction completed product by high performance liquid chromatography.

【0035】実施例3 合成例1のモノグリセライドケタール131.4g(0.4モ
ル)をフラスコに仕込み、濃硫酸40.45g(0.4モル)を3
0℃、2.7kPaで5.1時間にわたって滴下した。30℃、2.7k
Paで2.9時間熟成した後酸価を測定し、当量の48%KO
H水溶液と脱イオン水334.9gの中に反応終了物を氷冷
しながら添加した。得られたモノグリセライドサルフェ
ートK塩の高速液体クロマトグラフィーの組成を表1に
示す。
Example 3 A flask was charged with 131.4 g (0.4 mol) of the monoglyceride ketal of Synthesis Example 1, and 40.45 g (0.4 mol) of concentrated sulfuric acid was added to 3 parts of the flask.
The solution was added dropwise at 0.degree. 30 ℃, 2.7k
After aging for 2.9 hours at Pa, the acid value was measured and the equivalent of 48% KO
The finished product was added to 334.9 g of an H aqueous solution and deionized water while cooling with ice. Table 1 shows the composition of the obtained monoglyceride sulfate K salt by high performance liquid chromatography.

【0036】実施例4 合成例1のモノグリセライドケタール131.4g(0.4モ
ル)をフラスコに仕込み、90℃、2.7kPaで脱水した。冷
却後、発煙硫酸(SO3として30%含有)36.75g(0.4モ
ル)を30℃、2.7kPaで4時間にわたり滴下した。30℃、
2.7kPaで1時間熟成後酸価を測定し、当量の48%KOH
水溶液及び脱イオン水600gの中に氷冷下反応終了物を
添加した。得られたモノグリセライドサルフェートK塩
の高速液体クロマトグラフィーの組成を表1に示す。
Example 4 131.4 g (0.4 mol) of the monoglyceride ketal of Synthesis Example 1 was charged into a flask and dehydrated at 90 ° C. and 2.7 kPa. After cooling, 36.75 g (0.4 mol) of fuming sulfuric acid (containing 30% as SO 3 ) was added dropwise at 30 ° C. and 2.7 kPa over 4 hours. 30 ℃,
After aging for 1 hour at 2.7 kPa, the acid value was measured, and the equivalent of 48% KOH
The finished product was added to an aqueous solution and 600 g of deionized water under ice cooling. Table 1 shows the composition of the obtained monoglyceride sulfate K salt by high performance liquid chromatography.

【0037】実施例5 合成例1で得られたモノグリセライドケタール32.85g
(0.1モル)とヘプタン32.85gをフラスコに仕込み、30
℃、常圧で濃硫酸10.11g(0.1モル)を5時間にわたっ
て滴下した。その後30℃、常圧で2時間熟成し、ロータ
リーエバポレーターで30℃で脱溶媒した。このものの酸
価を測定し、当量の48%KOH水溶液と脱イオン水83.7
gに氷冷下脱溶媒物を添加した。得られたモノグリセラ
イドサルフェートK塩の高速液体クロマトグラフィーの
組成を表1に示す。
Example 5 32.85 g of the monoglyceride ketal obtained in Synthesis Example 1
(0.1 mol) and 32.85 g of heptane were charged into a flask, and 30
At room temperature and normal pressure, 10.11 g (0.1 mol) of concentrated sulfuric acid was added dropwise over 5 hours. Thereafter, the mixture was aged at 30 ° C. and normal pressure for 2 hours, and the solvent was removed at 30 ° C. using a rotary evaporator. The acid value of this was measured, and an equivalent amount of a 48% KOH aqueous solution and deionized water 83.7
The solvent was added to g under ice-cooling. Table 1 shows the composition of the obtained monoglyceride sulfate K salt by high performance liquid chromatography.

【0038】実施例6 合成例1で得られたモノグリセライドケタール32.85g
(0.1モル)とジメチルスルホキシド32.85gをフラスコ
に仕込み、30℃、常圧で濃硫酸10.11g(0.1モル)を5
時間にわたって滴下した。その後70℃、6.7kPaで3.5時
間反応させた。このものの酸価を測定し、当量の48%K
OH水溶液と脱イオン水50.9gに反応終了物を氷冷下添
加し、モノグリセライドサルフェートK塩を得た。高速
液体クロマトグラフィーの組成を表1に示す。
Example 6 32.85 g of the monoglyceride ketal obtained in Synthesis Example 1
(0.1 mol) and 32.85 g of dimethyl sulfoxide were charged into a flask, and 10.11 g (0.1 mol) of concentrated sulfuric acid was added at 30 ° C. and normal pressure.
Dropped over time. Thereafter, the reaction was carried out at 70 ° C. and 6.7 kPa for 3.5 hours. The acid value of this product was measured and the equivalent of 48% K
The finished product was added to an aqueous OH solution and 50.9 g of deionized water under ice cooling to obtain a monoglyceride sulfate K salt. Table 1 shows the composition of high performance liquid chromatography.

【0039】比較例1 C12モノグリセライド(太陽化学社製サンソフト750)2
7.44g(0.1モル)をフラスコに仕込み、50℃、6.7kPaで
濃硫酸10.11g(0.1モル)を1時間にわたって滴下し
た。50℃、6.7kPaで2時間熟成したところ、表1に示す
組成から明らかなように、脂肪酸エステルの分解が起こ
り、放置すると2相分離した。
[0039] Comparative Example 1 C 12 monoglyceride (manufactured by Taiyo Kagaku Co., Ltd. Sunsoft 750) 2
7.44 g (0.1 mol) was charged into a flask, and 10.11 g (0.1 mol) of concentrated sulfuric acid was added dropwise at 50 ° C. and 6.7 kPa over 1 hour. After aging for 2 hours at 50 ° C. and 6.7 kPa, as is clear from the composition shown in Table 1, the fatty acid ester was decomposed, and two phases were separated on standing.

【0040】[0040]

【表1】 [Table 1]

【0041】[0041]

【発明の効果】本発明の製造法により、比較的取り扱い
の容易な硫酸化剤を使って、必ずしも溶媒を必要とせず
に無機塩の少ないモノグリセライドサルフェートを製造
できる。しかも同時に生成するケトン又はアルデヒドを
回収再使用すれば、より安価な製造が可能となる。
According to the production method of the present invention, a monoglyceride sulfate having a small amount of inorganic salts can be produced by using a sulfating agent which is relatively easy to handle and does not necessarily require a solvent. Moreover, if the ketone or aldehyde produced at the same time is recovered and reused, the production can be performed at lower cost.

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】 一般式(1) 【化1】 (式中、R1は炭素数6〜22の飽和又は不飽和脂肪酸か
らカルボキシル基を除いた残基、R2及びR3は同一又は
異なって、水素原子、炭素数1〜8の直鎖又は分岐鎖の
アルキル基もしくはR2とR3が連結して環を形成する基
を示す。)で表されるモノグリセライドのアセタール又
はケタール(以下化合物(1)という)と硫酸化剤とを
反応させる、一般式(2)で表されるモノグリセライド
サルフェートの製造法。 【化2】 (式中、R1は前記と同じ意味を示し、Xは水素原子又
は−SO3Mを示し、Mは陽イオンを示す。)
1. A compound of the general formula (1) (Wherein, R 1 is a residue obtained by removing a carboxyl group from a saturated or unsaturated fatty acid having 6 to 22 carbon atoms, R 2 and R 3 are the same or different and are a hydrogen atom, a straight chain having 1 to 8 carbon atoms or A monoglyceride acetal or ketal (hereinafter referred to as compound (1)) represented by a branched alkyl group or a group in which R 2 and R 3 are linked to form a ring; A method for producing a monoglyceride sulfate represented by the general formula (2). Embedded image (In the formula, R 1 has the same meaning as described above, X represents a hydrogen atom or —SO 3 M, and M represents a cation.)
【請求項2】 化合物(1)と硫酸化剤とを反応させた
後、更に塩基成分で中和する、一般式(2)で表される
モノグリセライドサルフェートの製造法。
2. A method for producing monoglyceride sulfate represented by the general formula (2), wherein the compound (1) is reacted with a sulfating agent and then neutralized with a base component.
【請求項3】 化合物(1)と硫酸化剤とを反応させる
際に、反応系内を減圧にする、請求項1又は2記載の製
造法。
3. The process according to claim 1, wherein the pressure in the reaction system is reduced when reacting the compound (1) with the sulfating agent.
【請求項4】 化合物(1)が、グリセリンと一般式
(3) 【化3】 (式中、R2及びR3は前記の意味を示す。)で表される
ケトン類から一般式(4) 【化4】 (式中、R2及びR3は前記の意味を示す。)で表される
ジオキソラン化合物を得た後、一般式(5) R1COOR4 (5) (式中、R1は前記の意味を示し、R4は水素原子、炭素
数1〜3のアルキル基又は油脂からR1COO基を除い
た残基を示す。)で表される脂肪酸、その低級アルキル
エステル又は油脂でエステル化することにより得られた
ものである請求項1〜3のいずれか一項に記載の製造
法。
4. A compound (1) comprising glycerin and a compound represented by the following general formula (3): (Wherein, R 2 and R 3 have the same meanings as described above) from the ketones represented by the general formula (4). (In the formula, R 2 and R 3 have the above-mentioned meanings.) After obtaining a dioxolane compound represented by the general formula (5), R 1 COOR 4 (5) (wherein, R 1 has the above-mentioned meanings) And R 4 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a residue obtained by removing the R 1 COO group from an oil or fat.), And esterifying with a lower alkyl ester or an oil or fat thereof. The production method according to any one of claims 1 to 3, which is obtained by:
【請求項5】 化合物(1)が、グリセリンと一般式
(3)で表されるケトン類と一般式(5)で表される脂
肪酸、その低級アルキルエステル又は油脂とを混合して
反応させて得られたものである請求項1〜3のいずれか
一項に記載の製造法。
5. A compound (1) comprising a mixture of glycerin, a ketone represented by the general formula (3) and a fatty acid represented by the general formula (5), a lower alkyl ester thereof or a fat or oil, and reacted. The method according to any one of claims 1 to 3, which is obtained.
JP27383299A 1999-09-28 1999-09-28 Method for preparing monoglyceride sulfate Pending JP2001097942A (en)

Priority Applications (1)

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Family

ID=17533180

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Country Status (1)

Country Link
JP (1) JP2001097942A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002069068A (en) * 2000-08-29 2002-03-08 Kao Corp Method of preparing monoglyceride ketal
JP2007520459A (en) * 2003-12-19 2007-07-26 ザ プロクター アンド ギャンブル カンパニー Modified alkoxylated polyol compounds
JP2020011910A (en) * 2018-07-13 2020-01-23 株式会社Kri Method for producing sulfate compound

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002069068A (en) * 2000-08-29 2002-03-08 Kao Corp Method of preparing monoglyceride ketal
JP2007520459A (en) * 2003-12-19 2007-07-26 ザ プロクター アンド ギャンブル カンパニー Modified alkoxylated polyol compounds
JP2020011910A (en) * 2018-07-13 2020-01-23 株式会社Kri Method for producing sulfate compound
JP7077165B2 (en) 2018-07-13 2022-05-30 株式会社Kri Method for producing sulfate ester compound

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