JP3127480B2 - Method for producing aliphatic tertiary amine and surfactant - Google Patents

Method for producing aliphatic tertiary amine and surfactant

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Publication number
JP3127480B2
JP3127480B2 JP03106877A JP10687791A JP3127480B2 JP 3127480 B2 JP3127480 B2 JP 3127480B2 JP 03106877 A JP03106877 A JP 03106877A JP 10687791 A JP10687791 A JP 10687791A JP 3127480 B2 JP3127480 B2 JP 3127480B2
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JP
Japan
Prior art keywords
copper
hue
amine
tertiary amine
reaction
Prior art date
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Expired - Fee Related
Application number
JP03106877A
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Japanese (ja)
Other versions
JPH04230246A (en
Inventor
尚良 岡島
幹郎 中澤
康昭 小川
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.)
New Japan Chemical Co Ltd
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New Japan Chemical Co Ltd
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Application filed by New Japan Chemical Co Ltd filed Critical New Japan Chemical Co Ltd
Priority to JP03106877A priority Critical patent/JP3127480B2/en
Priority to KR1019910016574A priority patent/KR100211777B1/en
Publication of JPH04230246A publication Critical patent/JPH04230246A/en
Application granted granted Critical
Publication of JP3127480B2 publication Critical patent/JP3127480B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/90—Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/08—Monoamines containing alkyl groups having a different number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/20—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
    • C07C211/21—Monoamines
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Cosmetics (AREA)

Description

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

【０００１】[0001]

【産業上の利用分野】本発明は、脂肪族第３アミンの製
造方法及び当該方法により製造された脂肪族第３アミン
から誘導される界面活性剤に関する。The present invention relates to a method for producing an aliphatic tertiary amine and a surfactant derived from the aliphatic tertiary amine produced by the method.

【０００２】[0002]

【従来の技術】長鎖の脂肪族第３アミン、具体的には、
ジ長鎖アルキル（アルケニル）モノ短鎖アルキルアミン
又はトリ長鎖アルキル（アルケニル）アミンは、アミン
オキシド、アミン塩、四級アンモニウム塩及びアミノベ
タイン等の非イオン系、両性及び陽イオン系界面活性剤
の原料として重要な化合物であり、これらの界面活性剤
は、染色助剤、ヘアリンス剤、繊維柔軟剤、帯電防止
剤、殺菌剤、乳化剤等、広範囲な分野において用いられ
ている。2. Description of the Related Art Long-chain aliphatic tertiary amines, specifically,
Di long chain alkyl (alkenyl) mono short chain alkyl amines or tri long chain alkyl (alkenyl) amines are nonionic, amphoteric and cationic surfactants such as amine oxides, amine salts, quaternary ammonium salts and aminobetaines. These surfactants are important compounds as raw materials for these products, and these surfactants are used in a wide range of fields such as dyeing assistants, hair rinse agents, textile softeners, antistatic agents, bactericides, and emulsifiers.

【０００３】これらの界面活性剤を化粧品、香粧品及び
工業用製品の成分として使用する場合、特に化粧品や香
粧品の成分として使用するに際しては、より無色、無臭
に近いものが要求される。又、加熱安定性についても経
時変化のないものが求められる。色相が悪いと多量の着
色料を必要とし、又、要望する色調が出しにくいためで
ある。又、香料についても最近は添加量を減少させる傾
向があるにも拘らず、臭気あるいは異臭が強いと多量の
香料を使用しないと付香できない等の欠点がある。When these surfactants are used as components of cosmetics, cosmetics and industrial products, particularly when used as components of cosmetics and cosmetics, they are required to be more colorless and odorless. Further, it is required that the heating stability does not change with time. If the hue is poor, a large amount of colorant is required, and it is difficult to obtain a desired color tone. In addition, despite the tendency to reduce the amount of perfume recently, if the odor or off-flavor is strong, there is a drawback that the perfume cannot be perfumed unless a large amount of perfume is used.

【０００４】長鎖脂肪族第３アミンの代表的な製造方法
としては、脂肪酸とアンモニアとを出発原料とし、ニト
リルを経由する方法（例えば、油化学、28、(6) 379 (197
9)、ＵＳ 2,355,356、ＵＳ 2,784,232、ＧＢ 759,291、
以下「ニトリル法」という。）があるが、この場合に
は、生成物にニトリル臭が残存する他、着色し易い等の
欠点がある。[0004] As a typical method for producing a long-chain aliphatic tertiary amine, a method in which a fatty acid and ammonia are used as starting materials and via a nitrile (eg, Oil Chemistry , 28 , (6) 379 (197)
9), US 2,355,356, US 2,784,232, GB 759,291,
Hereinafter, it is referred to as “nitrile method”. However, in this case, the product has disadvantages such as remaining of a nitrile odor and easy coloring.

【０００５】一方、上記問題点を改善し得る方法とし
て、脂肪族アルコールとアンモニア又は脂肪族第１アミ
ンから直接目的物を製造する方法（以下「直接法」とい
う。）がある。この方法は、製造工程が簡易であって、
生成物の臭気が少ないという等の利点を有していること
からいろいろと検討がなされており、反応触媒の一種と
して銅系触媒が用いられてきた。On the other hand, as a method capable of solving the above problems, there is a method of directly producing a target product from an aliphatic alcohol and ammonia or an aliphatic primary amine (hereinafter, referred to as a "direct method"). This method has a simple manufacturing process,
Various studies have been made on the merits of having an advantage such as low odor of the product, and a copper-based catalyst has been used as a kind of reaction catalyst.

【０００６】従来の方法により製造された脂肪族第３ア
ミンには、しばしば適用した銅系触媒に起因する金属成
分が溶存することがある。この金属成分は、脂肪族第３
アミンやそれらの誘導体である界面活性剤、例えば対応
する四級アンモニウム塩等の加熱色相や経時的な色相の
安定性を低下させ、酸化劣化を促進する原因ともなり、
極力除去されていることが望ましい（事実、厚生省薬務
局審査第二課監修による化粧品種別原料基準では２０pp
m以下に規制されている）。[0006] In the aliphatic tertiary amine produced by the conventional method, a metal component derived from the applied copper-based catalyst is often dissolved. This metal component is an aliphatic third
Surfactants that are amines and their derivatives, such as the corresponding quaternary ammonium salts, reduce the stability of the heated hue and the hue over time, and also promote oxidation deterioration,
It is desirable that it be removed as much as possible.
m or less).

【０００７】しかしながら、汎用の精製手段である蒸留
等の手段を適用することができない高沸点の長鎖脂肪族
第３アミンについては、それに代わる適当な精製方法が
なく、精製が不十分となり、そのためこれらから誘導さ
れる界面活性剤は、着色したり臭気があったりして、こ
れらの改善が強く望まれていた。[0007] However, for a long-chain aliphatic tertiary amine having a high boiling point, to which a means such as distillation, which is a general-purpose purification means, cannot be applied, there is no suitable alternative purification method, and the purification becomes insufficient. Surfactants derived therefrom are colored or have an odor, and improvement of these has been strongly desired.

【０００８】これまでにも、触媒金属の溶出を防ぐ試み
はなされてきた。例えば、特開昭61−60636号には、担
体を含まない銅化合物と錫化合物とからなる混合触媒系
が開示されている。又、特開昭64−13060号では、触媒
として銅（酸化銅）と亜鉛（酸化亜鉛）アルカリ土類金
属塩基からなる混合触媒系が提案されている。[0008] Attempts have been made to prevent the elution of catalytic metals. For example, Japanese Patent Application Laid-Open No. 61-60636 discloses a mixed catalyst system comprising a copper compound and a tin compound containing no carrier. In Japanese Patent Application Laid-Open No. 64-13060, a mixed catalyst system comprising copper (copper oxide) and zinc (zinc oxide) alkaline earth metal base is proposed as a catalyst.

【０００９】上記の提案の如く、当該反応に有効で、且
つ金属の溶出が抑制された新たな触媒系を探索すること
も有意義と考えられるが、他方、工業的な側面を勘案し
たとき、特殊な触媒系に限定されることなく、一般に用
いられている銅系触媒、例えば銅−クロマイト系触媒を
も使用し得ることが汎用的な技術を確立する上で好まし
い。しかしながら、当該触媒系においては、金属の溶出
が顕著である。As described above, it is considered significant to search for a new catalyst system that is effective for the reaction and in which metal elution is suppressed, but on the other hand, when the industrial aspect is taken into consideration, special catalysts are considered. It is preferable to use a commonly used copper-based catalyst, for example, a copper-chromite-based catalyst, without being limited to a particular catalyst system, in order to establish a general-purpose technique. However, metal elution is remarkable in the catalyst system.

【００１０】[0010]

【発明が解決しようとする課題】本発明者らは、かかる
二律背反の課題を解決すべく、鋭意検討の結果、特殊な
触媒のみならず、一般的な銅系触媒であっても水素分圧
及びアンモニア又は脂肪族第１アミンの分圧等の反応条
件を制御することにより、（１）銅系触媒に由来する金
属の溶出を極度に抑制し、酸化安定性を著しく改善する
ことができること、（２）かかる脂肪族第３アミンから
誘導される各種の界面活性剤は、臭気、色相、経時安定
性とも改善されることを見い出し、かかる知見に基づい
て本発明を完成するに至った。The inventors of the present invention have conducted intensive studies in order to solve such a trade-off problem. As a result, not only special catalysts but also general copper-based catalysts have been developed. By controlling the reaction conditions such as the partial pressure of ammonia or an aliphatic primary amine, (1) the elution of the metal derived from the copper-based catalyst can be extremely suppressed, and the oxidation stability can be significantly improved; 2) Various surfactants derived from such aliphatic tertiary amines were found to have improved odor, hue, and stability over time, and the present invention was completed based on such findings.

【００１１】即ち、本発明は、汎用的で、且つ工業的に
有利な条件下で、銅系触媒由来の銅の溶出を防ぎ、高純
度で、且つ酸化安定性の良好な高品質の脂肪族第３アミ
ンを製造することができる新規有用な方法、及びかかる
方法により調製された脂肪族第３アミンから誘導される
高品質の界面活性剤を提供することを目的とする。That is, the present invention is intended to prevent the elution of copper derived from a copper-based catalyst under general-purpose and industrially advantageous conditions, and to provide a high-purity, high-quality aliphatic high-quality aliphatic oxidant. It is an object of the present invention to provide a novel and useful method by which a tertiary amine can be produced, and a high-quality surfactant derived from an aliphatic tertiary amine prepared by such a method.

【００１２】[0012]

【課題を解決するための手段】本発明に係る脂肪族第３
アミンの製造方法は、炭素数８〜３６の脂肪族アルコー
ルと、アンモニア又は炭素数１〜３の脂肪族第１アミン
（以下「原料アミン」と総称する。）とを水素気流下に
生成水を除去しながら加熱反応して一般式（Ｉ）で表さ
れる脂肪族第３アミンを製造するに当たり、触媒として
銅−クロマイト、銅−亜鉛酸化物、銅−モリブデン酸化
物、銅−タングステン酸化物、銅−ニッケル酸化物、銅
−クロム−亜鉛酸化物、銅酸化物及びこれらの酸化物の
バリウム変性体、マンガン変性体、コバルト変性体及び
ラネー銅から選ばれる１種又は２種以上の銅系触媒を用
い、水素分圧を６〜１００気圧とし、原料アミン分圧を
０.１気圧以下に制御することを特徴とする。According to the present invention, there is provided an aliphatic third compound according to the present invention.
The method for producing an amine is a method of producing an aliphatic alcohol having 8 to 36 carbon atoms and ammonia or an aliphatic primary amine having 1 to 3 carbon atoms (hereinafter, collectively referred to as “raw material amine”) under a stream of hydrogen to produce water. In producing the aliphatic tertiary amine represented by the general formula (I) by performing a heat reaction while removing, copper-chromite, copper-zinc oxide, copper-molybdenum oxide, copper-tungsten oxide, One or more copper catalysts selected from copper-nickel oxide, copper-chromium-zinc oxide, copper oxide and barium modified, manganese modified, cobalt modified and Raney copper of these oxides And controlling the hydrogen partial pressure to 6 to 100 atm and the raw material amine partial pressure to 0.1 atm or less.

【化１】［式中、Ｒ1、Ｒ2は、同一又は異なって、炭素
数８〜３６のアルキル基又はアルケニル基を表す。Ｒ3
は、炭素数１〜３のアルキル基又は炭素数８〜３６のア
ルキル基若しくはアルケニル基を表す。］Wherein R 1 and R 2 are the same or different and each represent an alkyl group or an alkenyl group having 8 to 36 carbon atoms. R 3
Represents an alkyl group having 1 to 3 carbon atoms or an alkyl group or alkenyl group having 8 to 36 carbon atoms. ]

【００１３】本発明において適用する原料アルコール
は、直鎖状又は分岐鎖状の炭素数８〜３６を有する飽和
又は不飽和の脂肪族アルコールである。具体的には、オ
クチルアルコール、ラウリルアルコール、ミリスチルア
ルコール、セチルアルコール、オレイルアルコール、ス
テアリルアルコール、ベヘニルアルコール、エルシルア
ルコール、２−ヘキシルデカノール、２−イソヘプチル
イソウンデカノール、２−オクチルドデカノール、２−
デシルテトラデカノール、２−セチルステアリルアルコ
ール並びにこれらの混合アルコール、チーグラー法によ
って得られるチーグラーアルコール、オキソ合成によっ
て得られるオキソアルコール等の各種のアルコールが例
示される。又、ポリエーテルアルコール、例えばアルキ
ル基（又はアルケニル基）の炭素数が８〜３６、オキシ
アルキレン基（炭素数２〜４）の付加モル数が１〜２０
程度のポリオキシアルキレンアルキル（又はアルケニ
ル）エーテル等も使用できる。The starting alcohol used in the present invention is a linear or branched saturated or unsaturated aliphatic alcohol having 8 to 36 carbon atoms. Specifically, octyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, behenyl alcohol, erucyl alcohol, 2-hexyl decanol, 2-isoheptyl isoundecanol, 2-octyl dodecanol, 2-octyl alcohol
Various alcohols such as decyltetradecanol, 2-cetylstearyl alcohol, mixed alcohols thereof, Ziegler alcohol obtained by Ziegler method, and oxo alcohol obtained by oxo synthesis are exemplified. The polyether alcohol, for example, the alkyl group (or alkenyl group) has 8 to 36 carbon atoms, and the oxyalkylene group (2 to 4 carbon atoms) has 1 to 20 additional moles.
Polyoxyalkylene alkyl (or alkenyl) ethers and the like can also be used.

【００１４】これらの原料アルコールと反応させる脂肪
族第１アミンは、炭素数１〜３のアルキル基を有するモ
ノアルキルアミンであり、特にモノメチルアミンが好ま
しい。The aliphatic primary amine to be reacted with these starting alcohols is a monoalkylamine having an alkyl group having 1 to 3 carbon atoms, and monomethylamine is particularly preferred.

【００１５】原料アミンの適用量としては、脂肪族第１
アミンの場合、原料アルコールに対して０.４倍モル以
上が好ましく、０.５倍モル以上あれば反応を完結する
ことができ、多くとも０.７倍モル以上は必要としな
い。又、アンモニアの場合は、原料アルコールに対し
０.３〜０.４倍モル程度である。The amount of the starting amine to be applied is selected from aliphatic primary
In the case of an amine, the amount is preferably at least 0.4 times the mole of the starting alcohol, and if the amount is at least 0.5 times the mole, the reaction can be completed. At most 0.7 times the mole is not required. In the case of ammonia, the amount is about 0.3 to 0.4 times the mole of the raw material alcohol.

【００１６】本発明において用いられる銅系触媒として
は、銅−クロマイト、銅−亜鉛酸化物、銅−モリブデン
酸化物、銅−タングステン酸化物、銅−ニッケル酸化
物、銅−クロム−亜鉛酸化物、銅酸化物及びこれらの酸
化物のバリウム変性体、マンガン変性体、コバルト変性
体及びラネー銅から選ばれる１種又は２種以上の触媒系
が挙げられる。The copper catalyst used in the present invention includes copper-chromite, copper-zinc oxide, copper-molybdenum oxide, copper-tungsten oxide, copper-nickel oxide, copper-chromium-zinc oxide, Copper oxide and one or more catalyst systems selected from barium-modified, manganese-modified, cobalt-modified and Raney copper of these oxides are exemplified.

【００１７】触媒は、一般的には、表面積を拡張し、且
つシンタリングの防止を目的として、アルミナ、シリカ
−アルミナ、ゼオライト等の担体上に担持して使用する
ことが多い。しかしながら、本発明方法に関しては、こ
れら担体物質により当該第３アミンへの銅金属の溶解が
促進され、酸化安定性が低下する傾向が認められるた
め、これらの触媒は、いずれも担体を含まない触媒系が
好ましい。In general, the catalyst is often used by being supported on a carrier such as alumina, silica-alumina, or zeolite for the purpose of expanding the surface area and preventing sintering. However, with respect to the method of the present invention, the dissolution of copper metal into the tertiary amine is promoted by these carrier substances, and the tendency of oxidative stability to decrease is recognized. Systems are preferred.

【００１８】かかる銅系触媒の添加量は、原料アルコー
ルに対して、通常０.５〜１０重量％、好ましくは１〜
５重量％程度の範囲内で所望の反応速度に応じて適宜選
択すればよい。The amount of the copper-based catalyst to be added is usually 0.5 to 10% by weight, preferably 1 to 10% by weight, based on the starting alcohol.
It may be appropriately selected within a range of about 5% by weight according to a desired reaction rate.

【００１９】反応に際して導入される水素は、銅系触媒
を活性化し、生成する水の除去を促進する上で必要であ
る。ここで用いられる水素ガスは、その一部に窒素、二
酸化炭素その他の不活性ガスを含んでいてもよい。The hydrogen introduced during the reaction is necessary for activating the copper-based catalyst and promoting removal of generated water. The hydrogen gas used here may partially contain nitrogen, carbon dioxide or other inert gas.

【００２０】反応圧力は、従来、大気圧程度が適当であ
り、加圧系で反応することは生成水の留出を困難にし、
且つ副生成物が増大するために不利であるとされてき
た。しかしながら、原料アルコールの転化率の大小に拘
らず、全反応段階を通じて原料アミン分圧を０.１気圧
以下に、より好ましくは０.０５気圧以下に制御し、水
素分圧を ６〜１００気圧、好ましくは８〜５０気圧程
度に制御することにより、望ましくない副生物（例え
ば、アルデヒドの縮合物又はアミンのアルキル基交換反
応や加水分解に伴って生ずる副生成物）を低減し得ると
ともに、反応生成物中に溶解する銅の含量を著しく抑制
することができる。Conventionally, the reaction pressure is suitably about atmospheric pressure, and the reaction in a pressurized system makes it difficult to distill off the produced water.
It has been disadvantageous because of an increase in by-products. However, regardless of the degree of conversion of the raw material alcohol, the partial pressure of the raw material amine is controlled to 0.1 atm or less, more preferably 0.05 atm or less, and the hydrogen partial pressure is set to 6 to 100 atm throughout the reaction steps. By controlling the pressure to preferably about 8 to 50 atm, it is possible to reduce undesirable by-products (for example, condensates of aldehydes or by-products generated by the alkyl group exchange reaction or hydrolysis of amines), The content of copper dissolved in the product can be significantly suppressed.

【００２１】水素分圧が６気圧未満では、原料アミンの
分圧を、たとえ０.１気圧以下に保っても副生成物が多
くなって脂肪族第３アミンの純度が低下するとともに、
当該第３アミン中への銅の溶解量が急激に増加する。
又、１００気圧を越える水素分圧を適用した場合には、
しかも特殊な耐圧設備を必要とするため経済上不利であ
る。When the partial pressure of hydrogen is less than 6 atm, even if the partial pressure of the starting amine is kept at 0.1 atm or less, the amount of by-products increases and the purity of the aliphatic tertiary amine decreases.
The amount of copper dissolved in the tertiary amine increases rapidly.
When a hydrogen partial pressure exceeding 100 atm is applied,
Moreover, it requires special pressure-resistant equipment, which is economically disadvantageous.

【００２２】水素ガス及び原料アミンの各分圧の制御
は、適当な調節弁を用いてそれぞれの供給速度を適宜選
択することにより容易に行うことができる。尚、原料ア
ミンの供給方法は、間欠的であっても連続的であっても
よい。The control of each partial pressure of the hydrogen gas and the raw material amine can be easily performed by appropriately selecting the respective supply speeds using an appropriate control valve. The method for supplying the raw material amine may be intermittent or continuous.

【００２３】水素ガスの導入量は、消費される水素量や
熱エネルギー、更にガスを循環使用する場合は、ガス循
環能力等工業的プロセスとしての成否を決定する上で重
要な因子である。即ち、副反応を抑制し、脂肪族第３ア
ミンの純度を高め、更には当該第３アミン中への銅の溶
解を低減するためには、多量の水素ガスを導入すること
が望ましいが、逆に設備が多大となり、エネルギー面か
らも不利である。かかる観点より、本発明方法における
水素ガスの導入量は、通常、原料アルコール１モル当た
り、採用する圧力下において常温換算して５〜１５０ｌ
／時間程度、好ましくは１０〜１００ｌ／時間程度が推
奨される。５ｌ／時間未満の速度では生成する水が反応
系から抜けにくく、第３アミン中への銅の溶解量が増大
し、目的物である第３アミンの純度が低下する傾向が認
められる。１５０ｌ／時間を越えて導入したとしても特
別に有意差は認められず、経済上不利である。The amount of hydrogen gas introduced is an important factor in determining the success or failure of an industrial process, such as the amount of hydrogen consumed, thermal energy, and, if the gas is circulated, the gas circulation capacity. That is, in order to suppress side reactions, increase the purity of the aliphatic tertiary amine, and further reduce the dissolution of copper in the tertiary amine, it is desirable to introduce a large amount of hydrogen gas. In addition, the equipment is enormous, which is disadvantageous in terms of energy. From this point of view, the amount of hydrogen gas introduced in the method of the present invention is usually 5 to 150 l in terms of normal temperature under the employed pressure per mole of raw material alcohol.
/ Hour, preferably about 10 to 100 l / hour. At a rate of less than 5 l / hour, the generated water is less likely to escape from the reaction system, the amount of copper dissolved in the tertiary amine increases, and the purity of the target tertiary amine tends to decrease. Even if introduced over 150 l / h, there is no particular significant difference, which is economically disadvantageous.

【００２４】反応温度は、１６０〜２６０℃程度、好ま
しくは１９０〜２４０℃程度である。反応温度は、反応
速度に影響するのみで、当該第３アミンの純度、収率及
び当該第３アミンへの銅の溶解等への影響は少ない。The reaction temperature is about 160-260 ° C, preferably about 190-240 ° C. The reaction temperature only affects the reaction rate, and has little effect on the purity and yield of the tertiary amine and the dissolution of copper in the tertiary amine.

【００２５】以下に、本発明に係る製造方法を具体的に
例示する。反応器下部に水素ガス導入口及び原料アミン
の導入口を、反応器上部に水素ガス、生成水及び過剰の
原料アミンの抜き出し口を備えた電磁式攪拌機付きオー
トクレーブに、脂肪族第１アルコールと銅系触媒を仕込
み、系内を窒素ガス等の不活性ガスで置換した後、水素
ガスを反応混合物中に導入し、調節弁を用いて反応系内
を所定の圧力下に制御しつつ、攪拌しながら加熱する。
所定温度に達した時点で原料アミンの供給を始める。反
応中は、原料アミンの分圧が常に０.１気圧以下になる
ように原料アミンの供給を制御する。Hereinafter, the manufacturing method according to the present invention will be specifically exemplified. An aliphatic primary alcohol and copper were placed in an autoclave equipped with a magnetic stirrer equipped with a hydrogen gas inlet and a raw material amine inlet at the lower part of the reactor, and a hydrogen gas, product water and excess raw material amine at the upper part of the reactor. After charging the system catalyst and replacing the inside of the system with an inert gas such as nitrogen gas, hydrogen gas is introduced into the reaction mixture, and stirred while controlling the inside of the reaction system under a predetermined pressure using a control valve. While heating.
When the temperature reaches the predetermined temperature, the supply of the raw material amine is started. During the reaction, the supply of the starting amine is controlled so that the partial pressure of the starting amine is always 0.1 atmosphere or less.

【００２６】反応器の抜き出し口から出た水素ガス、生
成水及び未反応原料アミン等の蒸気は冷却し、水素を主
成分とするガス状物と液状物に分離する。尚、原料アミ
ン分圧は、このガス状物中における原料アミン濃度をガ
スクロマトグラフィー、中和滴定法又は紫外線吸収測定
法等により求めることができる。The vapor of hydrogen gas, produced water, unreacted raw material amine and the like discharged from the outlet of the reactor is cooled and separated into a gaseous substance containing hydrogen as a main component and a liquid substance. The raw material amine partial pressure can be determined by measuring the raw material amine concentration in the gaseous substance by gas chromatography, neutralization titration, ultraviolet absorption measurement, or the like.

【００２７】液状物は分液して水相を除き、油状物は反
応系に戻す。ガス状物は、系外へ排出させながら反応す
ることもできるが、循環機により反応系に戻し、繰り返
し使用すれば原料アミンや水素ガスの消費量を少なくす
ることができるので好ましい。この場合、循環ガスは、
何等特別の精製処理を施すことなく反応が完結するまで
使用することができ、循環ガスの一部をパージしたり、
新たな水素を補ったりする必要はほとんどない。The liquid is separated to remove the aqueous phase, and the oil is returned to the reaction system. The gaseous substance can be reacted while being discharged out of the system. However, it is preferable to return the gaseous substance to the reaction system by a circulator and use it repeatedly, since the consumption of the raw material amine and hydrogen gas can be reduced. In this case, the circulating gas is
It can be used until the reaction is completed without any special purification treatment, purging part of the circulating gas,
There is almost no need to supplement with new hydrogen.

【００２８】尚、触媒は、通常、昇温中に還元され、活
性状態となるが、還元に高温を要する場合には予め還元
処理を施してから用いることが便利である。The catalyst is usually reduced during the temperature rise and becomes active. However, when a high temperature is required for the reduction, it is convenient to perform a reduction treatment in advance before use.

【００２９】反応が完結した後、オートクレーブから反
応物を取り出し、触媒を濾別する。次いで、減圧蒸留に
より低沸点物を除去する。After the reaction is completed, the reactants are removed from the autoclave and the catalyst is filtered off. Next, low-boiling substances are removed by distillation under reduced pressure.

【００３０】本発明方法は、バッチ式のみならず、連続
反応にも適用できる。例えば、縦長の多段槽反応器に下
部から原料アルコール、原料アミン、水素ガス及び触媒
を供給する気液並流法や、上部から原料アルコールと触
媒を、下部から水素ガスと原料アミンとを供給する気液
向流法等が採用できる。The method of the present invention can be applied not only to a batch type but also to a continuous reaction. For example, a gas-liquid co-current method of supplying raw material alcohol, raw material amine, hydrogen gas and a catalyst from the lower part to a vertically elongated multi-stage reactor, or supplying raw material alcohol and a catalyst from the upper part and hydrogen gas and a raw material amine from the lower part A gas-liquid countercurrent method or the like can be adopted.

【００３１】かくして得られた、ほぼ無色透明で銅金属
の溶存が抑制された高純度の脂肪族第３アミンは、非イ
オン界面活性剤、両性界面活性剤、陽イオン界面活性剤
等の各種界面活性剤の原料として有効なものである。The thus obtained high-purity aliphatic tertiary amine which is almost colorless and transparent and in which the dissolution of copper metal is suppressed, can be used for various types of surfactants such as nonionic surfactants, amphoteric surfactants and cationic surfactants. It is effective as a raw material for activators.

【００３２】ここで、かかる非イオン界面活性剤として
は、ジアルキルメチルアミンオキサイド、両性界面活性
剤しては、ジアルキルメチルアミノ酢酸ベタイン、ジア
ルキル−Ｎ−（２−ヒドロキシ−３−スルホプロピル）
アンモニウム、陽イオン界面活性剤としては、ジアルキ
ルジメチルアンモニウムハライド、ジアルキルメチルベ
ンジルアンモニウムハライド、ジアルキルメチルアンモ
ニウムエトサルフェート等を例示することができる。Here, the nonionic surfactant is dialkylmethylamine oxide, and the amphoteric surfactant is dialkylmethylaminoacetate betaine, dialkyl-N- (2-hydroxy-3-sulfopropyl).
Examples of ammonium and cationic surfactants include dialkyldimethylammonium halide, dialkylmethylbenzylammonium halide, and dialkylmethylammonium ethosulfate.

【００３３】これらの界面活性剤は、通常の方法で調製
できる。この調製物は、通常、水溶液あるいは固形状で
あるが、必要に応じてエタノール、イソプロピルアルコ
ール等の溶剤を使用することができる。These surfactants can be prepared by a usual method. This preparation is usually in the form of an aqueous solution or solid, but if necessary, a solvent such as ethanol or isopropyl alcohol can be used.

【００３４】かくして得られた界面活性剤は、柔軟剤、
リンス剤、コンディショニング剤、洗浄剤、繊維精錬
剤、染色助剤、帯電防止剤、殺菌剤、乳化・分散剤等、
広範囲な分野において使用される。The surfactant thus obtained comprises a softener,
Rinsing agent, conditioning agent, cleaning agent, fiber refining agent, dyeing aid, antistatic agent, bactericide, emulsifying / dispersing agent, etc.
Used in a wide range of fields.

【００３５】当該界面活性剤は、必要に応じて公知のそ
の他の非イオン界面活性剤（例えば、ポリオキシアルキ
レンアルキルエーテル、高級脂肪酸アルカノールアミド
等）、陰イオン界面活性剤（例えば、石鹸、アルキル硫
酸エステル塩、α−スルホ脂肪酸エステル塩、モノアル
キルリン酸塩等）、両性界面活性剤（例えば、アルキル
アミドベタイン等）を併用することができる。The surfactant may be, if necessary, other known nonionic surfactants (eg, polyoxyalkylene alkyl ethers, higher fatty acid alkanolamides, etc.), and anionic surfactants (eg, soaps, alkyl sulfates). Ester salts, α-sulfofatty acid ester salts, monoalkyl phosphates, etc.) and amphoteric surfactants (eg, alkyl amide betaines) can be used in combination.

【００３６】又、必要に応じて染料、香料、ビルダー、
防腐剤、キレート剤、緩衝剤、腐食防止剤等をその用途
に応じて適宜選択して配合することができる。If necessary, dyes, fragrances, builders,
Preservatives, chelating agents, buffers, corrosion inhibitors and the like can be appropriately selected and blended depending on the use.

【００３７】[0037]

【実施例】以下に実施例を掲げ、本発明を詳しく説明す
る。尚、各例において調製された脂肪族第３アミンの特
性は、以下の方法により測定評価した。銅の含量（ppm） ：原子吸光分析法による。色相 ：比色法により色相（ＡＰＨＡ）を測定。加熱色相 ：被験物５０ｇを１００mlのビーカーに入れ、
空気中において１００℃で３時間放置し、そのときの色
相を比色法（ＡＰＨＡ）により測定評価する。臭気 ：パネラーにより判定。色相の経時安定性 ：被験物を５０℃で３カ月間放置し、
そのときの色相変化（初期色相と経時色相）を目視にて
観察する。The present invention will be described in detail below with reference to examples. The properties of the aliphatic tertiary amine prepared in each example were measured and evaluated by the following methods. Copper content (ppm) : Determined by atomic absorption spectrometry. Hue : Hue (APHA) is measured by a colorimetric method. Heating hue : 50 g of the test substance was placed in a 100 ml beaker,
It is left at 100 ° C. for 3 hours in the air, and the hue at that time is measured and evaluated by a colorimetric method (APHA). Odor : Determined by panelists. Hue stability over time : The test article was left at 50 ° C. for 3 months,
The hue change (initial hue and temporal hue) at that time is visually observed.

【００３８】実施例１ 反応器下部に水素ガス導入口及びモノメチルアミンの導
入口を、反応器上部に水素、生成水及び過剰の原料アミ
ンの抜き出し口を備えた５００mlの電磁式攪拌機付きオ
ートクレーブに、ドデシルアルコール１８６ｇ（１モ
ル）と担体を含まない銅−クロマイト触媒３.７ｇとを
仕込み、系内を窒素ガスで置換した後、２０ｌ／時間の
速度で水素ガスを反応物中に導入し、水素分圧１０気圧
の条件下、攪拌しながら昇温した。系内の温度が１３０
℃に達した時点でモノメチルアミンの供給を開始した。
反応中におけるモノメチルアミンの供給は、抜き出しガ
ス中のモノメチルアミンの分圧が0.0005〜0.05気圧にな
るように制御しつつ行った。反応器の抜き出し口からで
たガス状物は冷却して気液分離し、ガス状物は反応系へ
循環した。又、液状物中の油層部分も反応系へ戻した。
反応器の温度が２２０℃に到達してから約２.５時間反
応してモノメチルジドデシルアミンを調製した。反応物
のアルコール転化率は９９.２％であり、この間におい
て使用したモノメチルアミンの使用量は０.５３モルで
あった。尚、水素ガスは、当該触媒の還元に消費された
量のみを補った。反応物から触媒を濾別し、減圧下で蒸
留を行い、少量の低沸点アミン等を除去した。得られた
反応生成物の組成をガスクロマトグラフィーにより分析
した結果、モノメチルジラウリルアミンの純度は９８.
５％であり、その収率（対原料アルコール、以下同様）
は９６.２％であった。この反応生成物の色相は１０、
銅の含量は０.０５ppmであった。又、加熱色相は１０で
あった。Example 1 A 500 ml autoclave equipped with a magnetic stirrer equipped with a hydrogen gas inlet and a monomethylamine inlet at the bottom of the reactor and hydrogen, product water and excess raw material amine at the top of the reactor was provided. After charging 186 g (1 mol) of dodecyl alcohol and 3.7 g of a copper-chromite catalyst containing no carrier, replacing the inside of the system with nitrogen gas, introducing hydrogen gas into the reaction product at a rate of 20 l / hour, The temperature was raised while stirring under the condition of a partial pressure of 10 atm. The temperature in the system is 130
When the temperature reached ° C, the supply of monomethylamine was started.
The supply of monomethylamine during the reaction was performed while controlling the partial pressure of monomethylamine in the extracted gas to be 0.0005 to 0.05 atm. The gaseous matter discharged from the outlet of the reactor was cooled and separated into gas and liquid, and the gaseous matter was circulated to the reaction system. The oil layer in the liquid was also returned to the reaction system.
The reaction was carried out for about 2.5 hours after the temperature of the reactor reached 220 ° C. to prepare monomethyldidodecylamine. The alcohol conversion of the reaction product was 99.2%, and the amount of monomethylamine used during this period was 0.53 mol. The hydrogen gas supplemented only the amount consumed for the reduction of the catalyst. The catalyst was separated from the reaction product by filtration and distilled under reduced pressure to remove a small amount of low-boiling amine and the like. As a result of analyzing the composition of the obtained reaction product by gas chromatography, the purity of monomethyldilaurylamine was 98.
5% and its yield (relative to the starting alcohol, hereinafter the same)
Was 96.2%. The hue of the reaction product is 10,
The copper content was 0.05 ppm. The heating hue was 10.

【００３９】実施例２ ステアリルアルコール２００ｇ（０.７４モル）及び担
体を含まない銅−クロマイト触媒４.０ｇを用いて、水
素分圧を８気圧に制御し、１５ｌ／時間の速度で水素ガ
スを導入した他は実施例１と同様にしてモノメチルジス
テアリルアミンを調製した。その結果、純度９８.７％
の目的物を９５.９％の収率で得た。この反応生成物の
色相は１０、銅の含量は０.０８ppmであった。又、加熱
色相は１０であった。Example 2 Using 200 g (0.74 mol) of stearyl alcohol and 4.0 g of a carrier-free copper-chromite catalyst, the hydrogen partial pressure was controlled at 8 atm, and hydrogen gas was supplied at a rate of 15 l / hour. A monomethyldistearylamine was prepared in the same manner as in Example 1 except for the introduction. As a result, purity 98.7%
Was obtained in a yield of 95.9%. The hue of the reaction product was 10, and the copper content was 0.08 ppm. The heating hue was 10.

【００４０】実施例３ 水素分圧を５０気圧に制御し、３０ｌ／時間の速度で水
素ガスを導入した他は実施例２と同様にしてモノメチル
ジステアリルアミンを調製した。その結果、純度９８.
４％の目的物を９６.４％の収率で得た。この反応生成
物の色相は１０、銅の含量は０.１ppmであった。又、加
熱色相は１０であった。Example 3 Monomethyldistearylamine was prepared in the same manner as in Example 2 except that the hydrogen partial pressure was controlled at 50 atm and hydrogen gas was introduced at a rate of 30 l / hour. As a result, purity 98.
4% of the desired product was obtained in a yield of 96.4%. The color of the reaction product was 10, and the copper content was 0.1 ppm. The heating hue was 10.

【００４１】実施例４ 水素分圧を１００気圧に制御し、５０ｌ／時間の速度で
水素ガスを導入した他は実施例２と同様にしてモノメチ
ルジステアリルアミンを調製したところ、純度９７.１
％の目的物が９５.４％の収率で得られた。この反応生
成物の色相は１０、銅の含量は０.４ppmであった。又、
加熱色相は２０であった。Example 4 Monomethyldistearylamine was prepared in the same manner as in Example 2 except that the hydrogen partial pressure was controlled at 100 atm and hydrogen gas was introduced at a rate of 50 l / hour. The purity was 97.1.
% Of the desired product was obtained in a yield of 95.4%. The hue of the reaction product was 10, and the copper content was 0.4 ppm. or,
The heating hue was 20.

【００４２】実施例５ オクチルアルコール２００ｇ（１.５４モル）及び担体
を含まない銅−クロマイト−バリウム変性触媒４.０ｇ
を用いた他は実施例１と同様にしてモノメチルジオクチ
ルアミンを調製した。その結果、純度９８.１％の目的
物を９５.２％の収率で得た。この反応生成物の色相は
１０、銅の含量は０.０４ppmであった。又、加熱色相は
１０であった。Example 5 200 g (1.54 mol) of octyl alcohol and 4.0 g of a carrier-free copper-chromite-barium modified catalyst
A monomethyldioctylamine was prepared in the same manner as in Example 1 except for using. As a result, the desired product having a purity of 98.1% was obtained in a yield of 95.2%. The hue of the reaction product was 10, and the copper content was 0.04 ppm. The heating hue was 10.

【００４３】実施例６ ミリスチルアルコール２００ｇ（０.９３モル）及び担
体を含まない銅−クロマイト−マンガン変性触媒４.０
ｇを用いた他は実施例１と同様にしてモノメチルジミリ
スチルアミンを調製した。その結果、純度９８.２％の
目的物を９６.０％の収率で得た。この反応生成物の色
相は１０、銅の含量は０.０７ppmであった。又、加熱色
相は１０であった。Example 6 200 g (0.93 mol) of myristyl alcohol and a carrier-free copper-chromite-manganese modified catalyst 4.0
Monomethyldimyristylamine was prepared in the same manner as in Example 1 except that g was used. As a result, the target product having a purity of 98.2% was obtained in a yield of 96.0%. The hue of the reaction product was 10, and the copper content was 0.07 ppm. The heating hue was 10.

【００４４】実施例７ ステアリルアルコール２００ｇ（０.７４モル）及び担
体を含まない銅−亜鉛酸化物触媒４.０ｇを用いた他は
実施例１と同様にしてモノメチルジステアリルアミンを
調製した。その結果、純度９７.９％の目的物を９５.３
％の収率で得た。この反応生成物の色相は１０、銅の含
量は０.０５ppmであった。又、加熱色相は１０であっ
た。Example 7 Monomethyldistearylamine was prepared in the same manner as in Example 1 except that 200 g (0.74 mol) of stearyl alcohol and 4.0 g of a copper-zinc oxide catalyst containing no carrier were used. As a result, 95.3% of the target product was 95.3% pure.
% Yield. The hue of the reaction product was 10, and the copper content was 0.05 ppm. The heating hue was 10.

【００４５】実施例８ ベヘニルアルコール２００ｇ（０.６１モル）及び担体
を含まない銅酸化物触媒４.０ｇを用いた他は実施例１
と同様にしてモノメチルジベヘニルアミンを調製した。
その結果、純度９８.３％の目的物を９５.７％の収率で
得た。この反応生成物の色相は１０、銅の含量は０.１
０ppmであった。又、加熱色相は１０であった。Example 8 Example 1 except that 200 g (0.61 mol) of behenyl alcohol and 4.0 g of a copper oxide catalyst containing no carrier were used.
Monomethyl dibehenylamine was prepared in the same manner as described above.
As a result, the desired product having a purity of 98.3% was obtained in a yield of 95.7%. The reaction product has a hue of 10 and a copper content of 0.1.
It was 0 ppm. The heating hue was 10.

【００４６】実施例９ 水添牛脂アルコール２００ｇ及びラネー銅触媒４.０ｇ
を用いた他は実施例１と同様にしてモノメチルジ水添牛
脂アルキルアミンを調製した。その結果、純度９７.８
％の目的物を９５.１％の収率で得た。この反応生成物
の色相は１０、銅の含量は０.５０ppmであった。又、加
熱色相は１０であった。Example 9 200 g of hydrogenated tallow alcohol and 4.0 g of Raney copper catalyst
A monomethyldihydrogenated tallow alkylamine was prepared in the same manner as in Example 1 except for using. As a result, the purity was 97.8.
% Of the desired product in a yield of 95.1%. The hue of the reaction product was 10, and the copper content was 0.50 ppm. The heating hue was 10.

【００４７】実施例１０ オクチルアルコール２００ｇ（１.５４モル）及び担体
を含まない銅−クロマイト触媒４.０ｇを用い、モノメ
チルアミンに代えてアンモニアを仕込んだ他は実施例１
と同様にして５時間反応し、トリオクチルアミンを調製
した。この間に用いたアンモニアは、２７ｇであった。
その結果、オクチルアルコールの転化率は９９.２％、
目的物の収率は９３.５％、その純度は９６.２％であっ
た。又、この反応生成物の色相は１０、銅の含量は０.
０５ppmであった。又、加熱色相は２０であった。Example 10 Example 1 was repeated except that 200 g (1.54 mol) of octyl alcohol and 4.0 g of a copper chromite catalyst containing no carrier were used and ammonia was used instead of monomethylamine.
The reaction was carried out for 5 hours in the same manner as described above to prepare trioctylamine. The amount of ammonia used during this period was 27 g.
As a result, the conversion of octyl alcohol was 99.2%,
The yield of the desired product was 93.5% and its purity was 96.2%. The reaction product had a hue of 10 and a copper content of 0.1.
It was 05 ppm. The heating hue was 20.

【００４８】実施例１１ 触媒として５０％担持の銅−亜鉛酸化物／ゼオライト触
媒４.０ｇを用いた他は実施例２と同様にしてモノメチ
ルジステアリルアミンを調製した。その結果、純度９
７.５％の目的物が９５.０％の収率で得られた。この反
応生成物中の銅の含量は５ppmであった。又、加熱色相
は３０であった。Example 11 Monomethyl distearylamine was prepared in the same manner as in Example 2 except that 4.0 g of a 50% supported copper-zinc oxide / zeolite catalyst was used as a catalyst. As a result, purity 9
7.5% of the desired product is obtained in a yield of 95.0%. The content of copper in this reaction product was 5 ppm. The heating hue was 30.

【００４９】実施例１２ ２−オクチルドデカノール１８１.２ｇ（０.６モル）及
び担体を含まない銅−亜鉛酸化物触媒４.０ｇを用いた
他は実施例１と同様にしてモノメチルジ（２−オクチル
ドデシル）アミンを調製した。その結果、純度９７.５
％の目的物を８０.２％の収率で得た。この反応生成物
の色相は１０、銅の含量は０.０５ppmであった。又、加
熱色相は１０であった。EXAMPLE 12 Monomethyldi (2-methyl-2- (2-methyl)-(2-methyl) (2-methyl) (2-methyl) Octyldodecyl) amine was prepared. As a result, the purity was 97.5.
% Of the desired product in a yield of 80.2%. The hue of the reaction product was 10, and the copper content was 0.05 ppm. The heating hue was 10.

【００５０】比較例１ モノメチルアミンの分圧を０.２〜０.５気圧とし、反応
時間を１.８時間とした他は実施例１と同様にしてモノ
メチルジドデシルアミンを調製した。その結果、純度８
５.５％の目的物が８０.４％の収率で得られた。この反
応生成物の銅の含量は１５０ppmであった。又、加熱色
相は１４０であった。Comparative Example 1 Monomethyldidodecylamine was prepared in the same manner as in Example 1 except that the partial pressure of monomethylamine was 0.2 to 0.5 atm and the reaction time was 1.8 hours. As a result, purity 8
5.5% of the desired product was obtained in a yield of 80.4%. The copper content of the reaction product was 150 ppm. The heating hue was 140.

【００５１】比較例２ 水素分圧を３気圧とした他は実施例２と同様にしてモノ
メチルジステアリルアミンを調製した。その結果、純度
９１.２％の目的物が８５.３％の収率で得られた。この
反応生成物の銅の含量は９５ppmであった。又、加熱色
相は１２０であった。Comparative Example 2 Monomethyl distearylamine was prepared in the same manner as in Example 2 except that the hydrogen partial pressure was changed to 3 atm. As a result, the desired product having a purity of 91.2% was obtained in a yield of 85.3%. The copper content of the reaction product was 95 ppm. The heating hue was 120.

【００５２】比較例３ ベヘニルアルコールを用いた他は比較例１と同様にして
モノメチルジべヘニルアミンを調製した。この反応生成
物の色相は１０、銅の含量は１５０ppm、加熱色相は１
４０であった。Comparative Example 3 Monomethyl dibehenylamine was prepared in the same manner as in Comparative Example 1 except that behenyl alcohol was used. The reaction product had a hue of 10, a copper content of 150 ppm, and a heated hue of 1
It was 40.

【００５３】例１ ５００mlの電磁式撹拌機付きオートクレーブ中に実施例
１で得られたモノメチルジラウリルアミン（全アミン価
１５２.９、第３アミン価１５１.４）７４.１ｇ（０.２
モル）、メチルクロライド１０ｇ（０.２モル）、炭酸
ナトリウム１３ｇ（原料アミンに対し０.６倍モル）及
びイソプロパノール／水混合物（混合重量比＝８０／２
０）７５ｇを仕込み、１００℃、３時間反応した。副生
した塩化ナトリウムを除去するために５０ｇ（対反応粗
物３０重量％）のイソプロパノールを加えて濾過し、最
終的にイソプロパノール／水系のテトラアルキルアンモ
ニウム型陽イオン界面活性剤（固形分８０％）を調製し
た。得られた界面活性剤の色相は２０、経時安定性良好
（初期色相２０、経時色相３０以下）、臭気良好（溶剤
臭あり）であった。 Example 1 74.1 g (0.2) of the monomethyldilaurylamine obtained in Example 1 (total amine value 152.9, tertiary amine value 151.4) in a 500 ml autoclave equipped with a magnetic stirrer.
Mol), 10 g (0.2 mol) of methyl chloride, 13 g of sodium carbonate (0.6 times mol with respect to the starting amine) and an isopropanol / water mixture (mixing weight ratio = 80/2).
0) 75 g was charged and reacted at 100 ° C. for 3 hours. To remove by-product sodium chloride, 50 g (30% by weight of the reaction crude) of isopropanol was added, followed by filtration. Finally, a tetraalkylammonium-type cationic surfactant of isopropanol / water system (solid content: 80%) Was prepared. The resulting surfactant had a hue of 20, good stability over time (initial hue, no more than 30 hue over time), and good odor (solvent odor).

【００５４】例２ 撹拌機、温度計及び冷却管を備えた１ｌの４ツ口フラス
コに実施例１により得られたモノメチルジラウリルアミ
ン７４.１ｇ（０.２モル）を含む水溶液４７４ｇを仕込
み、この中に７０℃、３０分でベンジルクロライド２６
ｇ（０.２モル）を滴下した。滴下終了後、更に７０℃
で３時間保持した後、９８℃で２時間反応を継続し、ト
リアルキルベンジルアンモニウム型陽イオン界面活性剤
水溶液（固形分２０％）を調製した。得られた界面活性
剤の色相は１５、経時安定性良好（初期色相１５、経時
色相２０）、臭気良好（異臭なし）であった。 Example 2 A 1 l four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 474 g of an aqueous solution containing 74.1 g (0.2 mol) of monomethyldilaurylamine obtained in Example 1, In this, benzyl chloride 26 at 70 ° C for 30 minutes.
g (0.2 mol) were added dropwise. After dropping, 70 ° C
After holding for 3 hours at 98 ° C., the reaction was continued for 2 hours to prepare an aqueous solution of a trialkylbenzylammonium-type cationic surfactant (solid content: 20%). The resulting surfactant had a hue of 15, good stability over time (initial hue 15 and hue over time 20), and good odor (no off-odor).

【００５５】例３ 実施例２で得られたモノメチルジステアリルアミン（全
アミン価１０５.５、第３アミン価１０４.４）１０７.
５ｇ（０.２モル）を適用した他は例１と同様にして、
イソプロパノール／水系のテトラアルキルアンモニウム
型陽イオン界面活性剤（固形分８０重量％）を調製し
た。得られた界面活性剤の色相は１０以下、経時安定性
は良好（初期色相１０以下、経時色相１５）、臭気良好
（溶剤臭は認められる）であった。 Example 3 Monomethyl distearylamine obtained in Example 2 (total amine value 105.5, tertiary amine value 104.4) 107.
Except that 5 g (0.2 mol) was applied, the same as in Example 1
An isopropanol / water-based tetraalkylammonium-type cationic surfactant (solid content: 80% by weight) was prepared. The resulting surfactant had a hue of 10 or less, good stability over time (initial hue 10 or less, hue 15 with time), and good odor (solvent odor was recognized).

【００５６】例４ 撹拌機、温度計及び冷却管を備えた４ツ口フラスコに実
施例２で得たモノメチルジステアリルアミン１０４ｇ
（０.２モル）とモノクロル酢酸ソーダ２３.３ｇ（０.
２モル）及び水８４０ｇを仕込み、８５℃で８時間反応
し、アルキルベタイン型両性界面活性剤水溶液（固形分
１５重量％）を調製した。得られた界面活性剤の色相は
１０以下、経時安定性は良好（初期色相１０以下、経時
色相１０）、臭気良好（異臭なし）であった。 Example 4 104 g of the monomethyldistearylamine obtained in Example 2 in a four-necked flask equipped with a stirrer, a thermometer and a condenser.
(0.2 mol) and 23.3 g of sodium monochloroacetate (0.2 mol).
2 mol) and 840 g of water, and reacted at 85 ° C. for 8 hours to prepare an aqueous solution of an alkyl betaine-type amphoteric surfactant (solid content: 15% by weight). The hue of the obtained surfactant was 10 or less, the stability with time was good (10 or less initial hue, 10 with time), and the odor was good (no off-odor).

【００５７】例５ 実施例６で得たモノメチルジミリスチルアミン（全アミ
ン価１３６、第３アミン価１３５.４）１６６ｇ（０.４
モル）を原料とした他は例４と同様にしてアルキルベタ
イン型両性界面活性剤水溶液（固形分１５重量％）を調
製した。得られた界面活性剤の色相は１０以下、経時安
定性は良好（初期色相１０以下、経時色相１０）、臭気
良好（異臭なし）であった。 Example 5 166 g of the monomethyldimyristylamine obtained in Example 6 (total amine value: 136, tertiary amine value: 135.4) (0.4 g)
Mol) as a raw material, and an aqueous solution of an alkyl betaine-type amphoteric surfactant (solid content 15% by weight) was prepared in the same manner as in Example 4 . The hue of the obtained surfactant was 10 or less, the stability with time was good (10 or less initial hue, 10 with time), and the odor was good (no off-odor).

【００５８】例６ 例４ と同様の反応器に実施例８で得たモノメチルジベヘ
ニルアミン（全アミン価９１.５、第３アミン価９０.
０）１２４.７ｇ（０.２モル）を含む水溶液１１３７ｇ
を仕込み、この中に９０℃、３時間で３５％過酸化水素
水２１.４ｇを徐々に滴下した。滴下終了後、更に９０
℃で４時間反応を継続した。その後、アルカリで中和
し、アルキルアミンオキサイド型非イオン界面活性剤水
溶液（固形分１０重量％）を調製した。得られた界面活
性剤の色相は１０以下、経時安定性は良好（初期色相１
０以下、経時色相１０）、臭気良好（異臭なし）であっ
た。 Example 6 In the same reactor as in Example 4 , the monomethyl dibehenylamine obtained in Example 8 (total amine value 91.5, tertiary amine value 90.
0) 1137 g of an aqueous solution containing 124.7 g (0.2 mol)
And 21.4 g of 35% aqueous hydrogen peroxide was gradually added dropwise at 90 ° C. for 3 hours. After dropping is completed, 90
The reaction was continued at 4 ° C. for 4 hours. Thereafter, the mixture was neutralized with an alkali to prepare an aqueous solution of an alkylamine oxide type nonionic surfactant (solid content: 10% by weight). The resulting surfactant has a hue of 10 or less and has good stability over time (initial hue 1).
0 or less, time-dependent hue 10), good odor (no off-flavor).

【００５９】例７ 例４ と同様の反応器に実施例１２で得たモノメチルジ
（２−オクチルドデシルアミン）（全アミン価１０１.
２、第３アミン価９９.０）８５ｇ（０.１５モル）を含
む水溶液１０２０ｇを仕込み、この中に７０℃、３０分
でベンジルクロライド１９ｇ（０.１５モル）を滴下し
た。滴下終了後、更に７０℃で４時間保持した後、９８
℃に昇温して２時間反応を継続し、トリアルキルベンジ
ルアンモニウム塩型陽イオン界面活性剤水溶液（固形分
１０重量％）を調製した。得られた界面活性剤の色相は
１５、経時安定性は良好（初期色相１５、経時色相２
０）、臭気良好（異臭なし）であった。 Example 7 Monomethyldi (2-octyldodecylamine) obtained in Example 12 (total amine value 101.1) was prepared in the same reactor as in Example 4 .
2,20 g (0.15 mol) of an aqueous solution containing 85 g (0.15 mol) of tertiary amine value 99.0 were charged, and 19 g (0.15 mol) of benzyl chloride was added dropwise at 70 ° C. for 30 minutes. After completion of the dropwise addition, the mixture was further kept at 70 ° C. for 4 hours,
The temperature was raised to ° C., and the reaction was continued for 2 hours to prepare a trialkylbenzylammonium salt type cationic surfactant aqueous solution (solid content: 10% by weight). The resulting surfactant has a hue of 15 and a good stability over time (initial hue 15, hue 2 over time)
0), good odor (no off-flavor).

【００６０】例８ 例４ と同様の反応器に実施例１０により得られたトリオ
クチルアミン（全アミン価１５８.０、第３アミン価１
５４.９）７２.４ｇ（０.２モル）を含む水溶液６３０
ｇを仕込み、この中に７０℃、３０分でベンジルクロラ
イド２６ｇ（０.２モル）を滴下した。滴下終了後、更
に７０℃で４時間保持した後、９８℃で２時間反応を継
続し、トリアルキルベンジルアンモニウム型陽イオン界
面活性剤水溶液（固形分１５％）を調製した。得られた
界面活性剤の色相は１５、経時安定性良好（初期色相１
５、経時色相２５）、臭気良好（異臭なし）であった。 Example 8 In the same reactor as in Example 4 , the trioctylamine obtained according to Example 10 (total amine value 158.0, tertiary amine value 1
54.9) Aqueous solution 630 containing 72.4 g (0.2 mol)
Then, 26 g (0.2 mol) of benzyl chloride was added dropwise at 70 ° C. for 30 minutes. After completion of the dropwise addition, the mixture was further maintained at 70 ° C. for 4 hours, and the reaction was continued at 98 ° C. for 2 hours to prepare a trialkylbenzylammonium-type cationic surfactant aqueous solution (solid content: 15%). The resulting surfactant has a hue of 15, and has good stability over time (initial hue 1).
5, hue 25) and good odor (no off-flavor).

【００６１】例９ 例４ と同様の反応器に実施例１０で得られたトリオクチ
ルアミン（全アミン価１５８.０、第３アミン価１５４.
９）７２.４ｇ（０.２モル）を原料とした他は例４と同
様にしてアルキルベタイン型両性界面活性剤水溶液（固
形分１５重量％）を調製した。得られた界面活性剤の色
相は１０、経時安定性は良好（初期色相１０、経時色相
１５）、臭気良好（異臭なし）であった。 Example 9 In the same reactor as in Example 4 , the trioctylamine obtained in Example 10 (total amine value 158.0, tertiary amine value 154.
9) An aqueous solution of an alkyl betaine-type amphoteric surfactant (solid content 15% by weight) was prepared in the same manner as in Example 4 except that 72.4 g (0.2 mol) of the raw material was used. The resulting surfactant had a hue of 10, a good stability over time (initial hue of 10, and a good hue of 15) and good odor (no off-odor).

【００６２】例１０ ステアリン酸とアンモニアとを原料としてニトリル法に
より調製されたモノメチルジステアリルアミン（色相１
５０、重金属０.５ppm、全アミン価１１０、第３アミン
価１０９）を適用した他は例３と同様にしてイソプロパ
ノール／水系のテトラアルキルアンモニウム型陽イオン
界面活性剤（固形分８０重量％）を調製した。得られた
界面活性剤の色相は１５０、経時安定性は初期色相１５
０、経時色相２５０で、溶剤臭の他にニトリル臭が認め
られた。 Example 10 Monomethyldistearylamine (hue 1) prepared by a nitrile method using stearic acid and ammonia as raw materials
50, heavy metal 0.5 ppm, total amine value 110, tertiary amine value 109), except that an isopropanol / water-based tetraalkylammonium-type cationic surfactant (solid content 80% by weight) was used in the same manner as in Example 3. Prepared. The hue of the obtained surfactant was 150, and the stability over time was 15 in the initial hue.
At 0 and a hue of 250, a nitrile smell was recognized in addition to the solvent smell.

【００６３】例１１ 例１０ で用いたモノメチルジステアリルアミンを適用し
た他は例３と同様にしてアルキルベタイン型両性界面活
性剤水溶液（固形分１５重量％）を調製した。得られた
界面活性剤の色相は５０、経時安定性は初期色相５０、
経時色相９０で、ニトリル臭が認められた。 Example 11 An aqueous solution of an alkyl betaine-type amphoteric surfactant (solid content: 15% by weight) was prepared in the same manner as in Example 3 except that the monomethyl distearylamine used in Example 10 was applied. The hue of the obtained surfactant was 50, and the stability over time was 50 as the initial hue.
At a hue of 90 over time, a nitrile smell was observed.

【００６４】例１２ 比較例３で得たモノメチルジベヘニルアミンを適用した
他は例６と同様にしてアルキルアミンオキサイド型非イ
オン界面活性剤水溶液（固形分１５重量％）を調製し
た。得られた界面活性剤の色相は２０、経時安定性は初
期色相２０、経時色相７０で、わずかにアミン臭が認め
られた。 Example 12 An aqueous solution of an alkylamine oxide type nonionic surfactant (solid content: 15% by weight) was prepared in the same manner as in Example 6 , except that the monomethyl dibehenylamine obtained in Comparative Example 3 was applied. The resulting surfactant had a hue of 20, and the stability with time was 20 in the initial hue and 70 in the hue, and a slight amine odor was observed.

【００６５】[0065]

【発明の効果】本発明に係る方法により、工業的に有利
な条件下で高純度で溶存金属が極度に抑制された脂肪族
第３アミンを製造することができる。かかる脂肪族第３
アミンを原料として適用することにより、色相、臭気、
経時安定性のいずれの特性においても飛躍的に改善され
た界面活性剤を調製することができる。According to the method of the present invention, an aliphatic tertiary amine having high purity and extremely low dissolved metal can be produced under industrially advantageous conditions. Such aliphatic third
By applying amine as a raw material, hue, odor,
Surfactants can be prepared that have dramatically improved stability over time in any of the properties.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ０１Ｊ 23/85 Ｂ０１Ｊ 25/00 23/889 Ｃ０７Ｃ 211/08 25/00 Ａ６１Ｋ 7/00 Ｂ Ｃ０７Ｃ 211/08 Ｃ // Ａ６１Ｋ 7/00 7/02 Ａ Ｃ０７Ｂ 61/00 ３００ 7/02 Ｃ１１Ｄ 3/30 Ｃ０７Ｂ 61/00 ３００ Ｂ０１Ｊ 23/74 ３２１Ｘ Ｃ１１Ｄ 3/30 23/84 ３１１Ｘ (56)参考文献 特開 平２−234（ＪＰ，Ａ) 特開 昭64−13060（ＪＰ，Ａ) 特開 昭59−222448（ＪＰ，Ａ) 特開 昭59−106441（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 209/16 C07C 211/03 - 211/08 C07B 61/00 300 ────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 7 Identification code FI B01J 23/85 B01J 25/00 23/889 C07C 211/08 25/00 A61K 7/00 B C07C 211/08 C // A61K 7 / 00 7/02 A C07B 61/00 300 7/02 C11D 3/30 C07B 61/00 300 B01J 23/74 321X C11D 3/30 23/84 311X (56) References JP-A-2-234 (JP, A) JP-A-64-13060 (JP, A) JP-A-59-222448 (JP, A) JP-A-59-106441 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) ) C07C 209/16 C07C 211/03-211/08 C07B 61/00 300

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 炭素数８〜３６の脂肪族アルコール
と、アンモニア又は炭素数１〜３の脂肪族第一アミンと
を水素気流下に生成水を除去しながら加熱反応して一般
式（１）で表される脂肪族第三アミンを製造するに当た
り、触媒として銅−クロマイト、銅−亜鉛酸化物、銅−
モリブデン酸化物、銅−タングステン酸化物、銅−ニッ
ケル酸化物、銅−クロム−亜鉛酸化物、銅酸化物及びこ
れらの酸化物のバリウム変性体、マンガン変性体、コバ
ルト変性体及びラネー銅から選ばれる１種又は２種以上
の銅系触媒を用い、水素分圧を６〜１００気圧とし、ア
ンモニア若しくは当該脂肪族第一アミンの分圧を０．１
気圧以下に制御することを特徴とする脂肪族第三アミン
の製造方法。 ［式中、Ｒ１、Ｒ２は、同一又は異なって、炭素数８〜
３６のアルキル基又はアルケニル基を表す。Ｒ３は、炭
素数１〜３のアルキル基又は炭素数８〜３６のアルキル
基又はアルケニル基を表す。］An aliphatic alcohol having 8 to 36 carbon atoms and ammonia or an aliphatic primary amine having 1 to 3 carbon atoms are heated and reacted under a hydrogen stream while removing generated water to obtain a compound represented by the general formula (1): In producing the aliphatic tertiary amine represented by, copper-chromite, copper-zinc oxide, copper-
Selected from molybdenum oxide, copper-tungsten oxide, copper-nickel oxide, copper-chromium-zinc oxide, copper oxide and barium-modified, manganese-modified, cobalt-modified and Raney copper of these oxides Using one or more copper-based catalysts, the hydrogen partial pressure is set to 6 to 100 atm, and the partial pressure of ammonia or the aliphatic primary amine is set to 0.1.
A method for producing an aliphatic tertiary amine, characterized in that the pressure is controlled to be at most atmospheric pressure. [Wherein, R 1 and R 2 are the same or different and each have 8 to 8 carbon atoms.
36 represents an alkyl group or an alkenyl group. R 3 represents an alkyl group having 1 to 3 carbon atoms or an alkyl group or alkenyl group having 8 to 36 carbon atoms. ]
JP03106877A 1990-09-20 1991-04-10 Method for producing aliphatic tertiary amine and surfactant Expired - Fee Related JP3127480B2 (en)

Priority Applications (2)

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JP03106877A JP3127480B2 (en) 1990-09-20 1991-04-10 Method for producing aliphatic tertiary amine and surfactant
KR1019910016574A KR100211777B1 (en) 1990-09-20 1991-09-20 Process for producing aliphatic amine

Applications Claiming Priority (3)

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JP2-253420 1990-09-20
JP25342090 1990-09-20
JP03106877A JP3127480B2 (en) 1990-09-20 1991-04-10 Method for producing aliphatic tertiary amine and surfactant

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JPH04230246A JPH04230246A (en) 1992-08-19
JP3127480B2 true JP3127480B2 (en) 2001-01-22

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KR100522822B1 (en) * 2003-11-18 2005-10-18 주식회사 엘지생활건강 Conditioning Sampoo Composition
JP5879123B2 (en) * 2011-12-27 2016-03-08 花王株式会社 Method for producing tertiary amine
CN103270015B (en) * 2010-12-27 2015-03-11 花王株式会社 Tertiary amine preparation process

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