JP4355073B2 - Cationic surfactant composition containing ester bond and method for preparing the same - Google Patents

Description

【０００４】
（式中、Ｒ₁は、炭素数１〜４のアルキル基、−ＣＨ₂ＣＨＲ₄ＯＨ、又は−ＣＨ₂ＣＨＲ₄ＯＣＯＲ₅、Ｒ₂は、（ＣＨ₂）nＮＨ₂（ｎは２〜３）、−ＣＨ₂ＣＨＲ₄ＯＨ又は−ＣＨ₂ＣＨＲ₄ＯＣＯＲ₅、Ｒ₃は、−ＣＨ₂ＣＨＲ₄ＯＨ、又は−ＣＨ₂ＣＨＲ₄ＯＣＯＲ₅、Ｒ₄は、ＨまたはＣＨ₃、Ｒ₅：Ｃ7〜Ｃ23のアルキル及びアルケニルの混合炭化水素基、Ｒ₆は、ＣＨ₃基又はＣ₂Ｈ₅基であるが、Ｒ₁、Ｒ₂及びＲ₃の少なくとも１つは、−ＣＨ₂ＣＨＲ₄ＯＣＯＲ₅基である、）
本発明は、又、不飽和脂肪酸メチルエステルを含む脂肪酸メチルエステルを水添して不飽和脂肪酸メチルエステルのトランス体/シス体の比率が２/９８〜９/９１の範囲内のものを調製し、次いでアルカノ−ルアミンと反応させてアルカノ−ルアミンエステルを合成し、得られたアルカノ−ルアミンエステルをジアルキル硫酸でカチオン化することを特徴とするカチオン界面活性剤組成物の製造方法を提供する。
本発明は、又、不飽和脂肪酸メチルエステルを含む脂肪酸メチルエステルを水添して不飽和脂肪酸メチルエステルのトランス体/シス体の比率が２/９８〜９/９１の範囲内のものを調製し、次いでアルカノ−ルアミンと反応させてアルカノ−ルアミンエステルを合成することを特徴とするアルカノ−ルアミンエステルの製造方法を提供する。
【０００５】
【発明の実施の形態】
本発明において原料として用いる脂肪酸低級アルキルエステルとしては、脂肪酸の炭素数が８〜２４（より好ましくは、炭素数が１０〜１８）の低級（好ましくは炭素数が１〜３、より好ましくは、メチル）であるのが好ましい。具体的には、牛脂脂肪酸低級アルキルエステル、パ−ム脂肪酸低級アルキルエステル、大豆油脂肪酸低級アルキルエステルに代表される動植物油由来のメチルエステルおよびオレイン酸メチルなどがある。
本発明では、この脂肪酸低級アルキルエステルを水素添加する。水素添加すると、脂肪酸低級アルキルエステル中の高度不飽和脂肪酸低級アルキルエステルが還元されてトランス型不飽和脂肪酸低級アルキルエステルに変わると同時に共存する着色物質等も還元されて非着色物質に変わることが予想される。
【０００６】
水素添加量は原料脂肪酸低級アルキルエステル中に残存する不飽和結合のトランス/シス比が２/９８〜９/９１（重量比）となるようにし、好ましくは３/９７〜９/９１である。この範囲内にすると、アルカノ−ルアミンエステルの着色改善効果が優れ、かつ脂肪酸低級アルキルエステル中のエステル組成が変化せず、最終用途の柔軟剤の物性に影響を与えないので好ましい。
尚、脂肪酸低級アルキルエステル中の不飽和脂肪酸低級アルキルエステル中は、２０〜９５質量％（以下、％と略称する）程度であるのが好ましく、より好ましくは、３０〜７０％である。
脂肪酸低級アルキルエステルの微量水素添加は、常法に従いニッケル触媒存在下、１８０〜２２０℃で水素消費量を制御して行うことができる。
アルカノ−ルアミンとしては、種々のものを用いることができ、例えば、炭素数５〜８であるのが好ましく、より好ましくは、炭素数５〜７である。又、例えば、一般式（３）や（４）で表されるものがあげられる。
【０００７】
【化３】

【０００８】
（式中、Ｒ₁、Ｒ₂及びＲ₃は、式（１）及び（２）におけるのと同様である。）
具体的には、トリエタノ−ルアミン、トリイソプロパノ−ルアミン、メチルジエタノ−ルアミン、メチルジイソプロパノ−ルアミン、３-（Ｎ，Ｎ-ジメチルアミノ）-1，2-プロピレングリコ−ル、Ｎ-メチルＮ-（２−ヒドロキシエチル）-1，３-プロパンジアミン、Ｎ-メチル-Ｎ-（ヒドロキシイソプロピル）-１，３-プロパンジアミン、Ｎ，Ｎ-ジヒドロキシエチル-１，３-プロパンジアミン、Ｎ，Ｎ-ジヒドロキシエチルエチレンジアミン、Ｎ，Ｎ-ジヒドロキシイソプロピル-１，３-プロパンジアミンおよびＮ，Ｎ-ジヒドロキシイソプロピルエチレンジアミンがある。これらは、単独でも又２種以上組み合わせて用いてもよい。
アルカノ−ルアミンエステルを合成するには、触媒を使用して脂肪酸メチルとアルカノ−ルアミンを減圧下、９０〜２２０℃に加熱し、副生低級アルコ−ルを除去して反応を完結させる方法によるのが好ましい。次いで触媒を中和し、濾過して中間アミンを得るのが好ましい（特開平05-148198号公報参照）。
アルカノ−ルアミンエステルのカチオン化は、ジアルキル硫酸を用いて行う。ここで、ジアルキル硫酸としては、それぞれのアルキル基の炭素数が１〜１０、好ましくは１〜３のジアルキル硫酸を用いるのがよい。特にジメチル硫酸やジエチル硫酸が好ましい。その使用量はアミンエステル１モルに対して０．９３〜１．００モルであるのがよい。また反応は米国特許3915867号公報に見られるように不純物の副生を少なくするために無溶媒状態で行うことが好ましい。なお反応温度は８０〜１２０℃で行うのがよい。
【０００９】
本発明では、このようにして製造した第４級アンモニウム塩をそのまま又は常法により精製若しくは単離し、カチオン界面活性剤組成物として用いることができる。
本発明により得られる第４級アンモニウム塩としては、上記式（１）又は（２）で表されるものが好ましい。式中、Ｒ₁は、炭素数１又は２のアルキル基、−ＣＨ₂ＣＨ₂ＯＨ、又は−ＣＨ₂ＣＨ₂ＯＣＯＲ₅、Ｒ₂及びＲ₃は、−ＣＨ₂ＣＨ₂ＯＨ、又は−ＣＨ₂ＣＨ₂ＯＣＯＲ₅、Ｒ₄は、ＨまたはＣＨ₃、Ｒ₅：Ｃ7〜Ｃ23のアルキル及びアルケニルの混合炭化水素基、Ｒ₆は、ＣＨ₃基又はＣ₂Ｈ₅基であるのが好ましく、Ｒ₁、Ｒ₂及びＲ₃の少なくとも１つは、又は−ＣＨ₂ＣＨＲ₄ＯＣＯＲ₅基である。上記式（３）及び（４）における好ましいものは、式（１）及び（２）におけると同様である。
本発明のカチオン界面活性剤組成物は、第４級アンモニウム塩に加えて、アルカノ−ルアミンエステルを１〜２５％程度含有してもよく、又水や有機溶媒などの溶媒を含有してもよい。
本発明のカチオン界面活性剤組成物は、柔軟剤の基材として好適に使用することができるが、さらに、毛髪用リンス基材としても用いることができる。
次に本発明を実施例により具体的に説明する。
【００１０】
【実施例】
実施例１
（１）微量水素添加したパ−ム脂肪酸メチルの合成
オレイン酸メチル７５質量％（以下、％と略称する）、リノ−ル酸メチル１６％およびステアリン酸メチル９％よりなるパ−ム脂肪酸メチル（ライオン株式会社、パステルM182：不飽和脂肪酸メチルのトランス/シス比率は０/１００）２．５Kgと市販の安定化ニッケル触媒２．５ｇ（０．１％/脂肪酸メチル）を４Lのオ−トクレイブに仕込み、窒素ガス置換を３回行った。ついで回転数を８００rpmにあわせ、温度1８５℃で約３Lの水素ガスを導入した。導入した水素が完全に消費されたら、冷却し、濾過助剤を使用して触媒を除き、微量水素添加したパ−ム脂肪酸メチルを得た。ケン化価より求めた分子量は２９５で、ＧＣから求めた不飽和脂肪酸メチルのトランス/シス質量比率は２．４/９７．６であった。又、色調（APHA）は８０であった。
（２）アルカノ−ルアミンエステルの合成
上記（１）で調製した微量水素添加したパ−ム脂肪酸メチル２６６ｇ（０．９モル）、ステアリン酸メチル（分子量２９８、ライオン（株）製パステルＭ１８００）２６８ｇ（０．９モル）及びトリエタノ−ルアミン１４９ｇ（１．０モル）、酸化マグネシウム０．２７ｇ、水酸化カリウム０．３７ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させて８時間反応させ、未反応メチルエステルが１％以下であることを確認した。ついで４０℃まで冷却し、触媒と等当量の硫酸１．０ｇを水で５０％に希釈して加えた。そのまま30分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ１５０であった。またアミン価より求めた分子量は６２２であった。
（３）カチオン界面活性剤の合成
上記（２）で合成した中間体アミン（分子量622）３１１ｇ（０．５モル）を温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで８０〜９０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を１１０℃に上昇し、３時間熟成した。
反応終了後約５１ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ１６０であった。
【００１１】
実施例２
（１）アルカノ−ルアミンエステルの合成
実施例１で調製した微量水素添加したパ−ム脂肪酸メチル２３６ｇ（０．８モル）、パステルＭ１８０、２３８ｇ（０．８モル）及びメチルジエタノ−ルアミン１１９ｇ（１．０モル）、酸化マグネシウム０．２４ｇ、水酸化カリウム０．３３ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。ついで４０℃まで冷却し、触媒と等当量の硫酸０.９ｇを水で５０％に希釈して加えた。そのまま３０分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ１４０であった。またアミン価より求めた分子量は５３６であった。
（２）カチオン界面活性剤の合成
上記（１）で合成した中間体アミン（分子量５３６）２６８ｇ（０．５モル）とエタノ−ル２６ｇを、温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで７０〜８０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を９０℃に上昇し、３時間熟成した。
反応終了後約５７ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ１４０であった
【００１２】
実施例３
（１）アルカノ−ルアミンエステルの合成
実施例１で調製した微量水素添加したパ−ム脂肪酸メチル２６６ｇ（０．９モル）、パステルＭ１８０、２６８ｇ(０．９モル)及びＮ−メチル、Ｎ−（２−ヒドロキシエチル）-１，３-プロパンジアミン１３４ｇ（１．０モル）、酸化マグネシウム０．２７ｇ、水酸化カリウム０．３７ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後、減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。ついで４０℃まで冷却し、触媒と等当量の１．０ｇの硫酸を水で５０％に希釈して加えた。そのまま３０分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ１６０であった。またアミン価より求めた分子量は６０２であった。
（２）カチオン界面活性剤の合成
上記（２）で合成した中間体アミン（分子量602）３０１ｇ（０．５モル）とエタノ−ル２９ｇを温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで７０〜８０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を９０℃に上昇し，３時間熟成した。
反応終了後約６２ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ１７０であった
【００１３】
実施例４
（１）微量水素添加したパ−ム脂肪酸メチルの合成
オレイン酸メチル７５％、リノ−ル酸メチル１６％およびステアリン酸メチル９％よりなるパ−ム脂肪酸メチル（ライオン株式会社、パステルM182）２．５Kgと市販の安定化ニッケル触媒２．５ｇ（０．１％/脂肪酸メチル）を４Lのオ−トクレイブに仕込み、窒素ガス置換を３回行った。次いで回転数を８００rpmにあわせ、温度1８５℃で約９Lの水素ガスを導入した。導入した水素が完全に消費されたら、冷却し、濾過助剤を使用して触媒を除き、微量水素添加したパ−ム脂肪酸メチルを得た。ケンカ価より求めた分子量は２９５で、GCから求めた不飽和脂肪酸メチルのトランス/シス比率は６．１/９３．１であった。色調（APHA）は７０であった。
（２）アルカノ−ルアミンエステルの合成
上記（２）で調製した微量水素添加したパ−ム脂肪酸メチル２６６ｇ（０．９モル）、パステルＭ１８０、２６８ｇ(０．９モル)及びトリエタノ−ルアミン１４９ｇ（１．０モル）、酸化マグネシウム０．２７ｇ、水酸化カリウム０．３７ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。次いで４０℃まで冷却し、触媒と等当量の１．０ｇの硫酸を水で５０％に希釈して加えた。そのまま30分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ１３０であった。またアミン価より測定した分子量は６２３であった。
（３）カチオン界面活性剤の合成
上記（３）で合成した中間体アミン（分子量623）３１２ｇ（０．５モル）を温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで８０〜９０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を１１０℃に上昇し、３時間熟成した。
反応終了後約５１ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ１４０であった。
【００１４】
実施例５：アルカノ−ルアミンエステルの合成
実施例４の（１）で調製した微量水素添加したパ−ム脂肪酸メチル２３６ｇ（０．８モル）、パステル１８０、２３８ｇ(０．８モル)及びメチルジエタノ−ルアミン１１９ｇ（１．０モル）、酸化マグネシウム０．２４ｇ、水酸化カリウム０．３３ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。次いで４０℃まで冷却し、触媒と等当量の０.９ｇの硫酸を水で５０％に希釈して加えた。そのまま３０分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ１３０であった。
【００１５】
実施例６：アルカノ−ルアミンエステルの合成
実施例４の（１）で調製した微量水素添加したパ−ム脂肪酸メチル２６６ｇ（０．９モル）、パステルＭ１８０、２６８ｇ(０．９モル)及びＮ−メチル、Ｎ−（２−ヒドロキシエチル）-１，３-プロパンジアミン１３４ｇ（１．０モル）、酸化マグネシウム０．３７ｇ、水酸化カリウム０．３７ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１L４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。次いで４０℃まで冷却し、触媒と等当量の１．０ｇの硫酸を水で５０％に希釈して加えた。そのまま３０分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ１４０であった。
【００１６】
実施例７
（１）微量水素添加したパ−ム脂肪酸メチルの合成
オレイン酸メチル７５％、リノ−ル酸メチル１６％およびステアリン酸メチル９％よりなるパ−ム脂肪酸メチル（ライオン株式会社、パステルM182）２．５Kgと市販の安定化ニッケル触媒２．５ｇ（０．１％/脂肪酸低級アルキルエステル）を４Lのオ−トクレイブに仕込み、窒素ガス置換を３回行った。次いで回転数を８００rpmにあわせ、温度1８５℃で約１２．４Lの水素ガスを導入した。導入した水素が完全に消費されたら、冷却し、濾過助剤を使用して触媒を除き、微量水素添加したパ−ム脂肪酸メチルを得た。ケンカ価より求めた分子量は２９５で、GCから求めた不飽和脂肪酸メチルのトランス/シス比率は８.８/９１.２であった。色調は（APHA）５０であった。
（２）アルカノ−ルアミンエステルの合成
上記（１）で調製した微量水素添加したパ−ム脂肪酸メチル２６６ｇ（０．９モル）、パステルＭ１８０、２６８ｇ(０．９モル)及びトリエタノ−ルアミン１４９ｇ（１．０モル）、酸化マグネシウム０．２７ｇ、水酸化カリウム０．３７ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。次いで５０℃まで冷却し、触媒と等当量の１．０ｇ硫酸を水で５０％に希釈して加えた。そのまま30分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ９０であった。またアミン価から求めた分子量は６２４であった。
（３）カチオン界面活性剤の合成
上記（３）で合成した中間体アミン（分子量624）３１２ｇ（０．５モル）を温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで８０〜９０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を１１０℃に上昇し，３時間熟成した。
反応終了後約５１ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ１００であった。
【００１７】
実施例８
（１）アルカノ−ルアミンエステルの合成
実施例７の（１）で調製した微量水素添加したパ−ム脂肪酸メチル２３６ｇ（０．８モル）、パステルＭ１８０、２３８ｇ(０．８モル)及びメチルジエタノ−ルアミン１１９ｇ（１．０モル）、酸化マグネシウム０．２４ｇ、水酸化カリウム０．３３ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１L４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。次いで５０℃まで冷却し、触媒と等当量の０.９ｇの硫酸を水で５０％に希釈して加えた。そのまま３０分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ８０であった。またアミン価より求めた分子量は５３８であった。
（２）カチオン界面活性剤の合成
上記（１）で合成した中間体アミン（分子量５３８）２６８ｇ（０．５モル）とエタノ−ル２６ｇを温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで７０〜８０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を９０℃に上昇し，３時間熟成した。
反応終了後約５８ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ９０であった
【００１８】
実施例９
（１）アルカノ−ルアミンエステルの合成
実施例８の（１）で調製した微量水素添加したパ−ム脂肪酸メチル２６６ｇ（０．９モル）、パステルＭ１８０、２６８ｇ(０．９モル)及びＮ−メチル、Ｎ−（２−ヒドロキシエチル）-１，３-プロパンジアミン１３４ｇ（１．０モル）、酸化マグネシウム０．２７ｇ、水酸化カリウム０．３７ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。ついで５０℃まで冷却し、触媒と等当量の１．０ｇの硫酸を水で５０％に希釈して加えた。そのまま３０分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ１００であった。またアミン価より求めた分子量は６０４であった。
（２）カチオン界面活性剤の合成
上記（１）で合成した中間体アミン（分子量604）３０２ｇ（０．５モル）とエタノ−ル２９ｇを温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで７０〜８０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を９０℃に上昇し，３時間熟成した。
反応終了後約６２ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ１１０であった。
【００１９】
比較例１
（１）アルカノ−ルアミンエステルの合成
パ−ム脂肪酸メチル（分子量２９４、ライオン株式会社製パステルＭ１８２）２６６ｇ（０．９モル）、パステルＭ１８０、２６８ｇ(０．９モル)及びトリエタノ−ルアミン１４９ｇ（１．０モル）、酸化マグネシウム０．２７ｇ、水酸化カリウム０．３７ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。次いで４０℃まで冷却し、触媒と等当量の１．０ｇ硫酸を水で５０％に希釈して加えた。そのまま30分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ３５０であった。またアミン価より求めた分子量は６２０であった。
（２）カチオン界面活性剤の合成
上記（１）１で合成した中間体アミン（分子量６２０）３１０ｇ（０．５モル）を温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで８０〜９０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を１１０℃に上昇し，３時間熟成した。
反応終了後約５９ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ４５０であった
【００２０】
比較例２
（１）アルカノ−ルアミンエステルの合成
パステルＭ１８２、２３６ｇ(０．８モル)、パステルＭ１８０、２３８ｇ（０．８モル）メチルジエタノ−ルアミン１１９ｇ（１．０モル）、酸化マグネシウム０．２４ｇ、水酸化カリウム０．３３ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。次いで５０℃まで冷却し、触媒と等当量の０.９ｇの硫酸を水で５０％に希釈て加えた。そのまま３０分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ３８０であった。またアミン価より求めた分子量は５３４であった．
（２）カチオン界面活性剤
上記（１）で合成した中間体アミン（分子量５３４）２６７ｇ（０．５モル）とエタノ−ル２６ｇを温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで７０〜８０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を９０℃に上昇し，３時間熟成した。
反応収量後約５６ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ５００以上であった。
【００２１】
比較例３
（１）アルカノ−ルアミンエステルの合成
パステルＭ１８２、２６６ｇ（０．９モル）、パステルＭ１８０、２６８ｇ(０．９モル)Ｎ−メチル、Ｎ−（２−ヒドロキシエチル）-１，３-プロパンジアミン１３４ｇ（１．０モル）、酸化マグネシウム０．２７ｇ、水酸化カリウム０．３７ｇおよび水２ｇを攪拌器、冷却器、温度計および減圧セットを備えた１Lの４つ口フラスコに入れ、窒素置換を行った後減圧し５００ｍｍHｇに維持した。次いで１９０℃まで加熱した。圧力を徐々に２０ｍｍHｇまで低下させ、８時間反応させ、未反応メチルエステルが１％以下であることを確認した。次いで５０℃まで冷却し、触媒と等当量の硫酸１．０ｇを水で５０％に希釈して加えた。そのまま３０分攪拌し、副生した無機塩を濾過し、アルカノ−ルアミンエステルを得た。色調（APHA）を測定したところ４００であった。またアミン価より測定した分子量は６００であった。
（２）カチオン界面活性剤の合成
上記（１）５で合成した中間体アミン（分子量600）３００ｇ（０．５モル）とエタノ−ル２９ｇを温度計、滴下ロ−ト及び冷却機を備えた4つ口フラスコに入れ窒素置換した。次いで７０〜８０℃に加熱し、ジメチル硫酸６１．７ｇ（０．４９モル）を１時間にわたり滴下した。滴下終了後反応物が増粘するので温度を９０℃に上昇し，３時間熟成した。
反応終了後約６２ｇのエタノ−ルを滴下しながら冷却し、エタノ−ル溶液を調製した。色調（APHA）を測定したところ５００以上であった
【００２２】
上記の実施例及び比較例における分析は、以下の方法により行った。
不飽和アルキル基のシス／トランス比率の測定
ＧＣにより測定した。
機種 ：Hitachi FID ガスクロG-3000
カラム： ＧＬサイエンス ＴＣ-７０（０．２５ｍｍ Ｉ．Ｄｘ３０）
温度 ：カラム１５０℃ → ２３０℃，昇温速度１０℃/毎分、
インジェクタ−＆デイテクタ-２４０℃
カラム圧力：1.0Kgf/ｃｍ2
未反応メチルエステル
ＧＣにより測定した。条件を次に示す。
（１）カラム：ULTRA-1、５ｍｘ0.2mmｘ0.11μｍ
（２）温度：デイテクタ-温度（FID）320℃、カラム150〜320℃、昇温速度１℃/分、１分、２２分保持（320℃）
（３） サンプル：BFTFAによりシリル化
（４） 内部標準：ベヘン酸メチル
アミン価の測定
自動滴定（HIRANUMA、TitstationTS-980型）を使用し、イソプロパノ−ルに溶解したサンプルを塩酸-ＩＰＡ規定液で滴定した。
色調（ＡＰＨＡ）の測定
比色計（日本電色工業製ＯＭＥ２０００型）を使用して測定した。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cationic surfactant composition having an ester bond in the molecule, a method for producing the same, and an alkano which is a production intermediate of the cationic surfactant, which can be suitably used as a softener substrate for clothing. -It relates to a method for producing a ruamine ester.
[Prior art]
Long-chain dialkyl type cationic surfactants are used as the base material for clothing softeners, but the rate of biodegradation after being discharged into the environment is slow. The use of active agents is increasing.
In order to produce these cationic surfactants, triethanolamine, methyldiethanolamine, 3- (N, N-dimethylamino) -1,2-propylene glycol and N-methyl-N- (2- Hydroxyethyl) -1,3-propanediamine and the like are acylated with a long chain fatty acid to synthesize an intermediate alkanolamine ester.
Subsequently, it is converted into a cationic compound with methyl chloride, dimethyl sulfate, diethyl sulfate or the like, or converted into a salt with a mineral acid or lower organic acid such as hydrochloric acid, sulfuric acid and phosphoric acid and used as a softener raw material.
In recent years, the use of fatty acid lower alkyl esters as acylating agents has increased. Acylation is carried out by converting a methyl ester and the aforementioned alkanolamine in the presence of a catalyst as shown in U.S. Pat.No. 3,915,867, German Published Patent No. Heating is performed by removing the by-produced lower alcohol from the reaction system. As a catalyst, sodium methylate, caustic soda, caustic potash, magnesium compound, etc. are used singly or as a mixture, so the quality of the raw fatty acid lower alkyl ester has a great influence on the color of the product and is synthesized. The color tone of the alkanolamine ester contributes to deterioration.
[0002]
[Problems to be solved by the invention]
An object of this invention is to provide the cationic surfactant composition excellent in the color tone.
Another object of the present invention is to provide an efficient method for producing a cationic surfactant composition having an excellent color tone.
Another object of the present invention is to provide a method for producing an alkanolamine ester having excellent color tone, which is an intermediate for producing the cationic surfactant.
[Means for Solving the Problems]
The present invention is able to synthesize alkanolamine ester having excellent color by adding a small amount of hydrogen of raw fatty acid lower alkyl ester without largely changing the composition of fatty acid lower alkyl ester, and then cationizing with dialkyl sulfuric acid. It was made based on the knowledge that it can be solved efficiently.
That is, the present invention provides at least one —OCOR in the molecule._FiveGroup (R_FiveIs a mixed hydrocarbon group of an alkyl group having 7 to 23 carbon atoms and an alkenyl group), and the ratio of stereoisomeric trans isomer / cis isomer in the alkenyl group is 2/98 to 9/91, Provided is a cationic surfactant composition comprising a quaternary ammonium salt represented by 1) and / or formula (2).
[0003]
[Chemical formula 2]

[0004]
(Wherein R₁Is an alkyl group having 1 to 4 carbon atoms, -CH₂CHR_FourOH or -CH₂CHR_FourOCOR_Five, R₂(CH₂) NNH₂(N is 2 to 3), -CH₂CHR_FourOH or -CH₂CHR_FourOCOR_Five, R_ThreeIs -CH₂CHR_FourOH or -CH₂CHR_FourOCOR_Five, R_FourIs H or CH_Three, R_Five: C7-C23 alkyl and alkenyl mixed hydrocarbon group, R₆Is CH_ThreeGroup or C₂H_FiveGroup R₁, R₂And R_ThreeAt least one of -CH₂CHR_FourOCOR_FiveIs the group)
In the present invention, a fatty acid methyl ester containing an unsaturated fatty acid methyl ester is hydrogenated to prepare a unsaturated fatty acid methyl ester having a trans / cis ratio in the range of 2/98 to 9/91. Then, the present invention provides a method for producing a cationic surfactant composition comprising reacting with an alkanolamine to synthesize an alkanolamine ester and cationizing the obtained alkanolamine ester with dialkyl sulfuric acid.
In the present invention, a fatty acid methyl ester containing an unsaturated fatty acid methyl ester is hydrogenated to prepare a unsaturated fatty acid methyl ester having a trans / cis ratio in the range of 2/98 to 9/91. Then, an alkanolamine ester is prepared by reacting with an alkanolamine to synthesize an alkanolamine ester.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The fatty acid lower alkyl ester used as a raw material in the present invention is a lower fatty acid having 8 to 24 carbon atoms (more preferably 10 to 18 carbon atoms), preferably 1 to 3 carbon atoms, more preferably methyl. ) Is preferred. Specific examples include beef tallow fatty acid lower alkyl esters, palm fatty acid lower alkyl esters, methyl esters derived from animal and vegetable oils represented by soybean oil fatty acid lower alkyl esters, and methyl oleate.
In the present invention, this fatty acid lower alkyl ester is hydrogenated. When hydrogenated, highly unsaturated fatty acid lower alkyl esters in fatty acid lower alkyl esters are reduced to trans-unsaturated fatty acid lower alkyl esters, and at the same time, coexisting colored substances are expected to be reduced to non-colored substances. Is done.
[0006]
The amount of hydrogenation is such that the trans / cis ratio of the unsaturated bond remaining in the raw fatty acid lower alkyl ester is 2/98 to 9/91 (weight ratio), preferably 3/97 to 9/91. Within this range, the coloration improving effect of the alkanolamine ester is excellent, the ester composition in the fatty acid lower alkyl ester does not change, and the physical properties of the final use softener are not affected, which is preferable.
The unsaturated fatty acid lower alkyl ester in the fatty acid lower alkyl ester is preferably about 20 to 95% by mass (hereinafter abbreviated as%), more preferably 30 to 70%.
The trace amount hydrogenation of the fatty acid lower alkyl ester can be performed by controlling the hydrogen consumption at 180 to 220 ° C. in the presence of a nickel catalyst according to a conventional method.
Various alkanolamines can be used. For example, the alkanolamine preferably has 5 to 8 carbon atoms, more preferably 5 to 7 carbon atoms. Moreover, for example, those represented by general formulas (3) and (4) can be mentioned.
[0007]
[Chemical 3]

[0008]
(Wherein R₁, R₂And R_ThreeIs the same as in equations (1) and (2). )
Specifically, triethanolamine, triisopropanolamine, methyldiethanolamine, methyldiisopropanolamine, 3- (N, N-dimethylamino) -1,2-propylene glycol, N-methylN -(2-hydroxyethyl) -1,3-propanediamine, N-methyl-N- (hydroxyisopropyl) -1,3-propanediamine, N, N-dihydroxyethyl-1,3-propanediamine, N, N -Dihydroxyethylethylenediamine, N, N-dihydroxyisopropyl-1,3-propanediamine and N, N-dihydroxyisopropylethylenediamine. These may be used alone or in combination of two or more.
In order to synthesize the alkanolamine ester, the fatty acid methyl and the alkanolamine are heated to 90 to 220 ° C. under reduced pressure using a catalyst to remove the by-product lower alcohol to complete the reaction. Is preferred. Next, the catalyst is preferably neutralized and filtered to obtain an intermediate amine (see JP-A-05-148198).
The cationization of the alkanolamine ester is carried out using dialkyl sulfuric acid. Here, as a dialkyl sulfuric acid, it is good to use the C1-C10 of each alkyl group, Preferably the dialkyl sulfuric acid of 1-3 is used. Particularly preferred is dimethyl sulfate or diethyl sulfate. The amount used is preferably 0.93 to 1.00 mole per mole of amine ester. The reaction is preferably carried out in a solvent-free state in order to reduce by-product impurities as seen in US Pat. No. 3,915,867. The reaction temperature is preferably 80 to 120 ° C.
[0009]
In the present invention, the quaternary ammonium salt thus produced can be used as a cationic surfactant composition as it is or after purification or isolation by a conventional method.
As a quaternary ammonium salt obtained by this invention, what is represented by the said Formula (1) or (2) is preferable. Where R₁Is an alkyl group having 1 or 2 carbon atoms, -CH₂CH₂OH or -CH₂CH₂OCOR_Five, R₂And R_ThreeIs -CH₂CH₂OH or -CH₂CH₂OCOR_Five, R_FourIs H or CH_Three, R_Five: C7-C23 alkyl and alkenyl mixed hydrocarbon group, R₆Is CH_ThreeGroup or C₂H_FivePreferably a group R₁, R₂And R_ThreeAt least one of or -CH₂CHR_FourOCOR_FiveIt is a group. Preferable ones in the above formulas (3) and (4) are the same as those in the formulas (1) and (2).
The cationic surfactant composition of the present invention may contain about 1 to 25% alkanolamine ester in addition to the quaternary ammonium salt, or may contain a solvent such as water or an organic solvent. .
The cationic surfactant composition of the present invention can be suitably used as a softener base material, but can also be used as a hair rinse base material.
Next, the present invention will be specifically described with reference to examples.
[0010]
【Example】
Example 1
(1)Synthesis of Palm Fatty Acid Methyl with Trace Hydrogenation
Palm fatty acid methyl consisting of 75% by mass of methyl oleate (hereinafter abbreviated as%), methyl linoleate 16% and methyl stearate 9% (Lion Corporation, Pastel M182: Trans / translation of unsaturated fatty acid methyl) A cis ratio of 0/100) 2.5 kg and a commercially available stabilized nickel catalyst 2.5 g (0.1% / fatty acid methyl) were charged into a 4 L autoclave, and nitrogen gas substitution was performed three times. Next, the rotation speed was adjusted to 800 rpm, and about 3 L of hydrogen gas was introduced at a temperature of 185 ° C. When the introduced hydrogen was completely consumed, it was cooled, the catalyst was removed using a filter aid, and a palm fatty acid methyl hydrogenated in a slight amount was obtained. The molecular weight determined from the saponification value was 295, and the trans / cis mass ratio of unsaturated fatty acid methyl determined from GC was 2.4 / 97.6. The color tone (APHA) was 80.
(2)Synthesis of alkanolamine esters
266 g (0.9 mol) of a methyl hydrogenated palm fatty acid prepared in (1) above, 268 g (0.9 mol) of methyl stearate (molecular weight 298, Pastel M1800 manufactured by Lion Corporation), and triethanolamine 149 g (1.0 mol), 0.27 g of magnesium oxide, 0.37 g of potassium hydroxide and 2 g of water were placed in a 1 L four-necked flask equipped with a stirrer, cooler, thermometer and reduced pressure set, and replaced with nitrogen. Then, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually lowered to 20 mmHg and reacted for 8 hours, and it was confirmed that the unreacted methyl ester was 1% or less. Then, the mixture was cooled to 40 ° C., and 1.0 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. The color tone (APHA) was measured and found to be 150. The molecular weight determined from the amine value was 622.
(3)Synthesis of cationic surfactants
311 g (0.5 mol) of the intermediate amine (molecular weight 622) synthesized in the above (2) was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and purged with nitrogen. Subsequently, it heated at 80-90 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. After completion of the dropwise addition, the reaction product thickened, so the temperature was raised to 110 ° C. and aged for 3 hours.
After completion of the reaction, about 51 g of ethanol was added dropwise and cooled to prepare an ethanol solution. It was 160 when the color tone (APHA) was measured.
[0011]
Example 2
(1)Synthesis of alkanolamine esters
236 g (0.8 mol) of palm hydrogenated methyl fatty acid prepared in Example 1, 238 g (0.8 mol) of pastel M180 and 119 g (1.0 mol) of methyldiethanolamine, 0.24 g of magnesium oxide Then, 0.33 g of potassium hydroxide and 2 g of water were put into a 1 L four-necked flask equipped with a stirrer, a cooler, a thermometer, and a vacuum set, and after substituting with nitrogen, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. Then, the mixture was cooled to 40 ° C., and 0.9 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. It was 140 when the color tone (APHA) was measured. The molecular weight determined from the amine value was 536.
(2)Synthesis of cationic surfactants
268 g (0.5 mol) of the intermediate amine (molecular weight 536) synthesized in the above (1) and 26 g of ethanol were placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler and purged with nitrogen. . Subsequently, it heated at 70-80 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. Since the reaction product thickened after completion of the dropwise addition, the temperature was raised to 90 ° C. and aged for 3 hours.
After completion of the reaction, about 57 g of ethanol was added dropwise and cooled to prepare an ethanol solution. It was 140 when the color tone (APHA) was measured.
[0012]
Example 3
(1)Synthesis of alkanolamine esters
266 g (0.9 mol) of methyl hydrogenated palm fatty acid prepared in Example 1, 268 g (0.9 mol) of pastel M180 and N-methyl, N- (2-hydroxyethyl) -1,3 -Place 134 g (1.0 mol) of propanediamine, 0.27 g of magnesium oxide, 0.37 g of potassium hydroxide and 2 g of water in a 1 L four-necked flask equipped with a stirrer, condenser, thermometer and vacuum set, After carrying out nitrogen substitution, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. Then, the mixture was cooled to 40 ° C., and 1.0 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. It was 160 when the color tone (APHA) was measured. The molecular weight determined from the amine value was 602.
(2)Synthesis of cationic surfactants
301 g (0.5 mol) of the intermediate amine (molecular weight 602) synthesized in the above (2) and 29 g of ethanol were placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and purged with nitrogen. Subsequently, it heated at 70-80 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. Since the reaction product thickened after completion of the dropwise addition, the temperature was raised to 90 ° C. and aged for 3 hours.
After completion of the reaction, about 62 g of ethanol was added dropwise to cool the mixture to prepare an ethanol solution. It was 170 when the color tone (APHA) was measured.
[0013]
Example 4
(1)Synthesis of Palm Fatty Acid Methyl with Trace Hydrogenation
2.5 kg of palm fatty acid methyl (Lion Corporation, Pastel M182) consisting of 75% methyl oleate, 16% methyl linoleate and 9% methyl stearate and 2.5 g of commercially available stabilized nickel catalyst (0. 1% / fatty acid methyl) was charged into a 4 L autoclave, and nitrogen gas substitution was performed three times. Next, the rotational speed was adjusted to 800 rpm, and about 9 L of hydrogen gas was introduced at a temperature of 185 ° C. When the introduced hydrogen was completely consumed, it was cooled, the catalyst was removed using a filter aid, and a palm fatty acid methyl hydrogenated in a slight amount was obtained. The molecular weight determined from the fighting value was 295, and the trans / cis ratio of unsaturated fatty acid methyl determined from GC was 6.1 / 93.1. The color tone (APHA) was 70.
(2) Synthesis of alkanolamine ester
A small amount of hydrogenated palm fatty acid methyl 266 g (0.9 mol) prepared in (2) above, pastel M180, 268 g (0.9 mol) and triethanolamine 149 g (1.0 mol), magnesium oxide 27 g, 0.37 g of potassium hydroxide, and 2 g of water were placed in a 1 L four-necked flask equipped with a stirrer, a cooler, a thermometer, and a vacuum set, and after substituting with nitrogen, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. It was then cooled to 40 ° C. and 1.0 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. The color tone (APHA) was measured and found to be 130. The molecular weight measured from the amine value was 623.
(3)Synthesis of cationic surfactants
312 g (0.5 mol) of the intermediate amine (molecular weight 623) synthesized in the above (3) was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and purged with nitrogen. Subsequently, it heated at 80-90 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. After completion of the dropwise addition, the reaction product thickened, so the temperature was raised to 110 ° C. and aged for 3 hours.
After completion of the reaction, about 51 g of ethanol was added dropwise and cooled to prepare an ethanol solution. It was 140 when the color tone (APHA) was measured.
[0014]
Example 5: Synthesis of alkanolamine ester
236 g (0.8 mol) of methyl hydrogenated palm fatty acid prepared in (1) of Example 4, 238 g (0.8 mol) of pastel 180 and 119 g (1.0 mol) of methyldiethanolamine, oxidation 0.24 g of magnesium, 0.33 g of potassium hydroxide and 2 g of water were put into a 1 L four-necked flask equipped with a stirrer, a cooler, a thermometer and a vacuum set, and after substituting with nitrogen, the pressure was reduced and maintained at 500 mmHg. . It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. The mixture was then cooled to 40 ° C., and 0.9 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. The color tone (APHA) was measured and found to be 130.
[0015]
Example 6: Synthesis of alkanolamine ester
266 g (0.9 mol) of a slightly hydrogenated palm fatty acid methyl prepared in (1) of Example 4, 268 g (0.9 mol) of pastel M180 and N-methyl, N- (2-hydroxyethyl) -1,3-propanediamine (134 g, 1.0 mol), magnesium oxide (0.37 g), potassium hydroxide (0.37 g) and water (2 g) were placed in a 1 L four-necked flask equipped with a stirrer, condenser, thermometer and vacuum set. Then, after nitrogen substitution, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. It was then cooled to 40 ° C. and 1.0 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. It was 140 when the color tone (APHA) was measured.
[0016]
Example 7
(1)Synthesis of Palm Fatty Acid Methyl with Trace Hydrogenation
2.5 kg of palm fatty acid methyl (Lion Corporation, Pastel M182) consisting of 75% methyl oleate, 16% methyl linoleate and 9% methyl stearate and 2.5 g of commercially available stabilized nickel catalyst (0. 1% / fatty acid lower alkyl ester) was charged into a 4 L autoclave, and nitrogen gas substitution was performed three times. Next, the rotational speed was adjusted to 800 rpm, and about 12.4 L of hydrogen gas was introduced at a temperature of 185 ° C. When the introduced hydrogen was completely consumed, it was cooled, the catalyst was removed using a filter aid, and a palm fatty acid methyl hydrogenated in a slight amount was obtained. The molecular weight determined from the fighting value was 295, and the trans / cis ratio of unsaturated fatty acid methyl determined from GC was 8.8 / 91.2. The color tone was (APHA) 50.
(2)Synthesis of alkanolamine esters
A small amount of hydrogenated palm fatty acid methyl 266 g (0.9 mol) prepared in (1) above, pastel M180, 268 g (0.9 mol) and triethanolamine 149 g (1.0 mol), magnesium oxide 27 g, 0.37 g of potassium hydroxide, and 2 g of water were placed in a 1 L four-necked flask equipped with a stirrer, a cooler, a thermometer, and a vacuum set, and after substituting with nitrogen, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. The mixture was then cooled to 50 ° C., and 1.0 g sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. The color tone (APHA) was measured and found to be 90. The molecular weight determined from the amine value was 624.
(3)Synthesis of cationic surfactants
312 g (0.5 mol) of the intermediate amine (molecular weight 624) synthesized in the above (3) was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and purged with nitrogen. Subsequently, it heated at 80-90 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. Since the reaction product thickened after completion of the dropwise addition, the temperature was raised to 110 ° C. and aged for 3 hours.
After completion of the reaction, about 51 g of ethanol was added dropwise and cooled to prepare an ethanol solution. The color tone (APHA) was measured and found to be 100.
[0017]
Example 8
(1)Synthesis of alkanolamine esters
236 g (0.8 mol) of methyl hydrogenated palm fatty acid prepared in (1) of Example 7, 238 g (0.8 mol) of pastel M180 and 119 g (1.0 mol) of methyldiethanolamine, oxidation 0.24 g of magnesium, 0.33 g of potassium hydroxide and 2 g of water were put into a 1 L four-necked flask equipped with a stirrer, a cooler, a thermometer and a vacuum set, and after nitrogen substitution, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. Then it was cooled to 50 ° C. and 0.9 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. The color tone (APHA) was measured and found to be 80. The molecular weight determined from the amine value was 538.
(2)Synthesis of cationic surfactants
268 g (0.5 mol) of the intermediate amine (molecular weight 538) synthesized in the above (1) and 26 g of ethanol were placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and purged with nitrogen. Subsequently, it heated at 70-80 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. Since the reaction product thickened after completion of the dropwise addition, the temperature was raised to 90 ° C. and aged for 3 hours.
After completion of the reaction, about 58 g of ethanol was added dropwise and cooled to prepare an ethanol solution. The color tone (APHA) measured was 90.
[0018]
Example 9
(1)Synthesis of alkanolamine esters
266 g (0.9 mol) of a slightly hydrogenated palm fatty acid methyl prepared in (1) of Example 8, 268 g (0.9 mol) of pastel M180 and N-methyl, N- (2-hydroxyethyl) -1,4-propanediamine 134g (1.0mol), magnesium oxide 0.27g, potassium hydroxide 0.37g and 2g water 1L 4 necks equipped with stirrer, cooler, thermometer and vacuum set The flask was placed in a flask, purged with nitrogen, and then reduced in pressure and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. The mixture was then cooled to 50 ° C., and 1.0 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. The color tone (APHA) was measured and found to be 100. The molecular weight determined from the amine value was 604.
(2)Synthesis of cationic surfactants
302 g (0.5 mol) of the intermediate amine (molecular weight 604) synthesized in the above (1) and 29 g of ethanol were placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and the atmosphere was replaced with nitrogen. Subsequently, it heated at 70-80 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. Since the reaction product thickened after completion of the dropwise addition, the temperature was raised to 90 ° C. and aged for 3 hours.
After completion of the reaction, about 62 g of ethanol was added dropwise to cool the mixture to prepare an ethanol solution. The color tone (APHA) was measured and found to be 110.
[0019]
Comparative Example 1
(1) Synthesis of alkanolamine ester
Palm fatty acid methyl (molecular weight 294, Pastel M182 manufactured by Lion Corporation) 266 g (0.9 mol), pastel M180, 268 g (0.9 mol) and triethanolamine 149 g (1.0 mol), magnesium oxide 27 g, 0.37 g of potassium hydroxide, and 2 g of water were placed in a 1 L four-necked flask equipped with a stirrer, a cooler, a thermometer, and a vacuum set, and after substituting with nitrogen, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. The mixture was then cooled to 40 ° C., and 1.0 g sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. It was 350 when the color tone (APHA) was measured. The molecular weight determined from the amine value was 620.
(2) Synthesis of cationic surfactant
The intermediate amine (molecular weight 620) 310 g (0.5 mol) synthesized in the above (1) 1 was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and purged with nitrogen. Subsequently, it heated at 80-90 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. Since the reaction product thickened after completion of the dropwise addition, the temperature was raised to 110 ° C. and aged for 3 hours.
After completion of the reaction, about 59 g of ethanol was added dropwise and cooled to prepare an ethanol solution. The color tone (APHA) measured was 450.
[0020]
Comparative Example 2
(1)Synthesis of alkanolamine esters
Pastel M182, 236 g (0.8 mol), pastel M180, 238 g (0.8 mol) methyldiethanolamine 119 g (1.0 mol), magnesium oxide 0.24 g, potassium hydroxide 0.33 g and water 2 g were stirred. The flask was placed in a 1 L four-necked flask equipped with a cooler, a thermometer, and a reduced pressure set, and after nitrogen substitution, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. The mixture was then cooled to 50 ° C., and 0.9 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. It was 380 when the color tone (APHA) was measured. The molecular weight determined from the amine value was 534.
(2) Cationic surfactant
267 g (0.5 mol) of the intermediate amine (molecular weight 534) synthesized in the above (1) and 26 g of ethanol were placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and the atmosphere was replaced with nitrogen. Subsequently, it heated at 70-80 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. Since the reaction product thickened after completion of the dropwise addition, the temperature was raised to 90 ° C. and aged for 3 hours.
After the reaction yield, the solution was cooled while adding dropwise about 56 g of ethanol to prepare an ethanol solution. The color tone (APHA) was measured and found to be 500 or more.
[0021]
Comparative Example 3
(1)Synthesis of alkanolamine esters
Pastel M182, 266 g (0.9 mol), Pastel M180, 268 g (0.9 mol) N-methyl, N- (2-hydroxyethyl) -1,3-propanediamine 134 g (1.0 mol), magnesium oxide 0.27 g, 0.37 g of potassium hydroxide, and 2 g of water were put into a 1 L four-necked flask equipped with a stirrer, a cooler, a thermometer, and a vacuum set, and after substituting with nitrogen, the pressure was reduced and maintained at 500 mmHg. It was then heated to 190 ° C. The pressure was gradually reduced to 20 mmHg and reacted for 8 hours to confirm that the unreacted methyl ester was 1% or less. Next, the mixture was cooled to 50 ° C., and 1.0 g of sulfuric acid equivalent to the catalyst was diluted to 50% with water and added. The mixture was stirred as it was for 30 minutes, and the by-produced inorganic salt was filtered to obtain an alkanolamine ester. The color tone (APHA) measured was 400. The molecular weight measured from the amine value was 600.
(2) Synthesis of cationic surfactant
The intermediate amine (molecular weight 600) 300 g (0.5 mol) synthesized in (1) 5 above and 29 g of ethanol were placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler and purged with nitrogen. . Subsequently, it heated at 70-80 degreeC, and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. Since the reaction product thickened after completion of the dropwise addition, the temperature was raised to 90 ° C. and aged for 3 hours.
After completion of the reaction, about 62 g of ethanol was added dropwise to cool the mixture to prepare an ethanol solution. The color tone (APHA) measured was 500 or more.
[0022]
The analysis in said Example and a comparative example was performed with the following method.
Measurement of cis / trans ratio of unsaturated alkyl groups
Measured by GC.
Model: Hitachi FID gas chromatograph G-3000
Column: GL Science TC-70 (0.25mm I.Dx30)
Temperature: Column 150 ° C. → 230 ° C., heating rate 10 ° C./min,
Injector & Detector-240 ℃
Column pressure: 1.0Kgf / cm2
Unreacted methyl ester
Measured by GC. The conditions are as follows:
(1) Column: ULTRA-1, 5mx0.2mmx0.11μm
(2) Temperature: Detector-temperature (FID) 320 ° C., column 150-320 ° C., heating rate 1 ° C./min, 1 minute, 22 minutes hold (320 ° C.)
(3) Sample: Silylated with BFTFA
(4) Internal standard: methyl behenate
Measurement of amine value
Using automatic titration (HIRANUMA, Titstation TS-980 type), a sample dissolved in isopropanol was titrated with hydrochloric acid-IPA normal solution.
Measurement of color tone (APHA)
It measured using the colorimeter (Nippon Denshoku Industries OME2000 type | mold).

Claims (2)

Hydrogenation to fatty acid lower alkyl esters containing 8-24 unsaturated fatty acid lower alkyl esters derived from animal and vegetable oils results in a stereoisomeric trans / cis mass ratio of unsaturated fatty acid lower alkyl esters of 2 / 98-9. And then reacting with an alkanolamine to synthesize an alkanolamine ester, and the resulting alkanolamine ester is cationized with dialkylsulfuric acid to give at least one —OCOR ₅ group (R ₅ is a mixed hydrocarbon group of an alkyl group having 7 to 23 carbon atoms and an alkenyl group), and the mass ratio of the stereoisomeric trans isomer / cis isomer in the alkenyl group is 2/98 to 9/91. A cationic surfactant composition comprising a quaternary ammonium salt represented by formula (1) and / or formula (2).

(In the formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, —CH ₂ CHR ₄ OH, or —CH ₂ CHR ₄ OCOR ₅ , R ₂ is — (CH ₂ ) nNH ₂ (n is 2 to 3). ), - CH ₂ CHR ₄ OH or _{-CH 2 CHR 4 OCOR 5, R} 3 is, -CH ₂ CHR ₄ OH, or _{-CH 2 CHR 4 OCOR 5, R} 4 is, H or CH _3, R _5: C7 alkyl and mixed hydrocarbon group having alkenyl ~C23, R ₆ is a CH ₃ group or a C ₂ H ₅ group, at least one of R _1, R ₂ and R _3, -CH ₂ CHR ₄ OCOR ₅ Group.) Stereoisomeric structure of the unsaturated fatty acid lower alkyl esters by hydrogenation in the fatty acid lower alkyl esters containing 8-24 unsaturated fatty acid lower alkyl ester derived from animal or vegetable oil trans form / cis form mass ratio of 2 / 98-9 / 91 were prepared and then reacted with an alkanolamine by combining the alkanolamine ester and the resulting alkanolamine esters characterized by cationized with dialkyl sulfate, at least one -OCOR ₅ groups in the molecule ( R ₅ has a mixed hydrocarbon group of an alkyl group having 7 to 23 carbon atoms and an alkenyl group, and the mass ratio of the stereoisomeric trans isomer / cis isomer in the alkenyl group is 2/98 to 9/91. A quaternary ammonium salt represented by formula (1) and / or formula (2): Way .

(In the formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, —CH ₂ CHR ₄ OH, or —CH ₂ CHR ₄ OCOR ₅ , R ₂ is — (CH ₂ ) nNH ₂ (n is 2 to 3). ), - CH ₂ CHR ₄ OH or _{-CH 2 CHR 4 OCOR 5, R} 3 is, -CH ₂ CHR ₄ OH, or _{-CH 2 CHR 4 OCOR 5, R} 4 is, H or CH _3, R _5: C7 alkyl and mixed hydrocarbon group having alkenyl ~C23, R ₆ is a CH ₃ group or a C ₂ H ₅ group, at least one of R _1, R ₂ and R _3, -CH ₂ CHR ₄ OCOR ₅ Group.)