JP2004075668A - Method for producing amide amine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an amide amine and an amide group-containing surfactant containing a small amount of a diamide and being low in cloudiness. <P>SOLUTION: This method for producing the amide amine is to react a fatty acid with a diamine; the fatty acid is made to react with the diamine in 0.3-0.9 molar times to 1 mole fatty acid at 130-170°C and subsequently at 10-50°C further higher temperature to react the residual diamine. The method for producing the amide group-containing surfactant is to bring the obtained amide amine to be amphoteric, quaternary or oxidized. <P>COPYRIGHT: (C)2004,JPO

Description

【０００６】
（式中、Ｒはココナッツ油脂肪酸等の脂肪酸残基を示す。）
上記のようなジアミドが存在した場合、有効成分含量が減るだけでなく、ジアミド中の３級アミド基の加水分解による２級アミンが発生し、また、上記ジアミドは、低温保存時に、濁り物質として析出するという問題がある。
【０００７】
アミドアミンは、具体的には柔軟剤の基剤として有用であるが、上記のようなジアミドが多量に存在した場合には、柔軟剤組成物を低温で保存した時に濁りが生じるという問題がある。
【０００８】
また、特許文献２には、Ｎ，Ｎ−ジメチル−１，３−プロパンジアミンを脂肪酸または脂肪酸留分と１４０〜２００℃で反応させることが記載されているが、アミド化時に、アミンを一括仕込みで反応させているため、比較的高温の反応（１７０〜２００℃）では、大量のアミンが、生成する水と共に系外に留去され、反応が十分に進行しない。低温で反応を行う方法として、特許文献３に記載されているように、過剰のアミンと脂肪酸を仕込み、徐々に温度を上昇させていく方法が採用されている。しかし比較的低温（１４０〜１６０℃）の反応でも、アミンの系外への留出は避けられず、しかも反応時間が長く効率的ではない。
【０００９】
【特許文献１】
特開２０００−１９１６１４号
【特許文献２】
米国特許第３，２２５，０７４号明細書
【特許文献３】
国際公開第９８／４７８６０号パンフレット
【００１０】
【発明が解決しようとする課題】
本発明の課題は、ジアミド含量が少なく、濁りの少ない、アミドアミン及びアミド基含有界面活性剤の効率的な製造法を提供することにある。
【００１１】
【課題を解決するための手段】
本発明者らは、脂肪酸とジアミンとを２段階で反応させることにより、アミド化時に、ジアミドの生成を抑制し、またアミンの系外への留出を抑制できることを見いだした。
【００１２】
本発明は、脂肪酸とジアミンを反応させてアミドアミンを製造する方法であって、脂肪酸と、脂肪酸１モルに対し０．３〜０．９モル倍のジアミンを１３０〜１７０℃の温度で反応させた後、更に１０〜５０℃高い温度で、残りのジアミンを反応させる、アミドアミンの製造法、並びに得られたアミドアミンを、両性化、４級化あるいは酸化する、アミド基含有界面活性剤の製造法を提供する。
【００１３】
【発明の実施の形態】
本発明に用いられる脂肪酸としては、一般式（Ｉ）で表される脂肪酸が挙げられる。
【００１４】
Ｒ^１ＣＯＯＨ　　（Ｉ）
（式中、Ｒ^１は炭素数７〜２３の直鎖又は分岐鎖のアルキル基、アルケニル基又はヒドロキシアルキル基を示す。）
具体的には、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ベヘン酸、エルカ酸、１２−ヒドロキシステアリン酸や、ヤシ油脂肪酸、綿実油脂肪酸、とうもろこし油脂肪酸、牛脂脂肪酸、ババス油脂肪酸、パーム核油脂肪酸、大豆油脂肪酸、アマニ油脂肪酸、ヒマシ油脂肪酸、オリーブ油脂肪酸、鯨油脂肪酸等の植物油又は動物油脂肪酸が挙げられる。これらの中では、Ｒ^１が炭素数９〜１９の直鎖アルキル基であるものが好ましく、更に炭素数９〜１７の直鎖アルキル基であるものが好ましい。
【００１５】
本発明に用いられるジアミンとしては、一般式（ＩＩ）　で表されるジアミンが好ましい。
【００１６】
【化５】

【００１７】
（式中、Ｒ^２は水素原子、炭素数１〜６の直鎖又は分岐鎖のアルキル基又はアルケニル基を示し、Ｒ^３はヘテロ原子又はカルボニル基から選ばれる少なくとも１つで置換されていてもよい、炭素数１〜８のアルキレン基を示し、Ｒ^４及びＲ^５は同一でも異なっていてもよい、炭素数１〜６の直鎖又は分岐鎖のアルキル基を示す。）
一般式（ＩＩ）で表されるジアミンとしては、ジメチルアミノプロピルアミン、ジメチルアミノエチルアミン、ジエチルアミノプロピルアミン、ジエチルアミノエチルアミン等が挙げられ、ジメチルアミノプロピルアミンが好ましい。
【００１８】
またジアミンとしては、その中に含まれる副生物（例えば、一般式（ＩＩ）において、Ｒ^４及び／又はＲ^５が、水素原子に置き換わっている化合物）の量が少ないジアミンを用いるのが、ジアミドの生成を抑制する観点から好ましい。
【００１９】
本発明においては、まず脂肪酸と、脂肪酸１モルに対し０．３〜０．９モル倍、好ましくは０．４〜０．８モル倍のジアミンを、１３０〜１７０℃、好ましくは１４０〜１６０℃の温度で反応させた後、更に１０〜５０℃、好ましくは１０〜３０℃高い温度で、残りのジアミンを反応させる。残りのジアミンは、一括して加えて反応させてもよいし、徐々に加えて反応させてもよい。なお、この反応におけるトータルの脂肪酸とジアミンとのモル比は、脂肪酸：ジアミン＝１：１〜１：２が好ましく、１：１〜１：１．５が更に好ましい。
【００２０】
上記のような本発明のアミド化反応により、ジアミド含量の少ないアミドアミンを製造することができる。
【００２１】
本発明の製造法により得られるアミドアミンとしては、一般式（ＩＩＩ）で表される化合物が好ましい。
【００２２】
【化６】

【００２３】
（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は前記の意味を示す。）
本発明で得られるアミドアミンは、更に従来公知の方法で両性化、４級化、酸化等の反応を行うことにより、ジアミド含量の少ないアミド基含有界面活性剤を製造することができる。
【００２４】
このようなアミド基含有界面活性剤としては、一般式（ＩＶ）、（Ｖ）、（ＶＩ）又は（ＶＩＩ）で表される化合物が挙げられ、一般式（ＩＶ）又は（Ｖ）で表されるベタインが好ましい。
【００２５】
【化７】

【００２６】
（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は前記の意味を示し、Ｒ^６は炭素数１〜４の直鎖又は分岐鎖のアルキレン基、Ｒ^７は炭素数１〜６の直鎖又は分岐鎖のアルキル基又はヒドロキシアルキル基、Ｘ⁻は、ハロゲンイオン、アルキル硫酸イオン等の陰イオンを示す。）
本発明において、アミドアミンの両性化は、公知の方法で行うことができ、例えば、上記のようなアミド化反応により得られた一般式（ＩＩＩ）で表されるアミドアミンに、一般式（Ｘ）
ＹＲ^６ＣＯＯＺ　　（Ｘ）
（式中、Ｙはハロゲン原子、Ｚは水素原子又はアルカリ金属を示し、Ｒ^６は前記の意味を示す。）
で表されるモノハロアルキルカルボン酸又はその塩、あるいは３−クロロ−２−ヒドロキシプロピルスルホン酸又はその塩を付加反応させることにより、ジアミド含量の少ない一般式（ＩＶ）又は（Ｖ）で表されるベタインを得ることができる。
【００２７】
一般式（Ｘ）で表されるモノハロアルキルカルボン酸又はその塩としては、モノクロロ酢酸、モノブロモ酢酸、モノクロロプロピオン酸、モノブロモプロピオン酸又はそれらのナトリウム塩、カリウム塩等が挙げられるが、モノクロロ酢酸又はその塩が好ましい。アミドアミンに対するモノハロアルキルカルボン酸又はその塩、あるいは３−クロロ−２−ヒドロキシプロピルスルホン酸又はその塩の量は、１〜３モル倍が好ましく、１〜１．１５モル倍が更に好ましい。
【００２８】
本発明において、アミドアミンと、一般式（Ｘ）で表されるモノハロアルキルカルボン酸又はその塩、あるいは３−クロロ−２−ヒドロキシプロピルスルホン酸又はその塩との付加反応は、例えばアミドアミンとモノハロアルキルカルボン酸又はその塩とを、ベタイン化が終了するまではｐＨを８〜１０に保ち、その後は残存するモノハロアルキルカルボン酸塩の加水分解を促進するためにｐＨ１１．５〜１３の範囲に保って反応させることが好ましく、反応温度は５０〜１００　℃の範囲が好ましい。反応は常圧でも加圧下で行っても良い。
【００２９】
また本発明において、アミドアミンの４級化や酸化は、従来公知の方法で行うことができる。例えば、上記のようなアミド化反応により得られた一般式（ＩＩＩ）で表されるアミドアミンに、塩化メチル、ジメチル硫酸等の４級化剤を反応させることにより、ジアミド含量の少ない一般式（ＶＩ）で表される第４級アンモニウム塩を得ることができ、一般式（ＩＩＩ）で表されるアミドアミンを、過酸化水素、ペルオキシ硫酸又はフェントン試薬等で酸化することにより、ジアミド含量の少ない一般式（ＶＩＩ）で表されるアミンオキサイドを得ることができる。
【００３０】
【実施例】
例中の％は特記しない限り重量基準である。尚、以下の例において、ジアミド含量は、以下のＨＰＬＣ条件で、含有量既知のジアミドを標品として用い、絶対検量線法により定量した。
【００３１】
＜ＨＰＬＣ条件＞
カラム：Ｌ−　ＣＯＬＵＭＮ　ＯＤＳ（４．６ｍｍφ×１５０ｍｍ，５μｍ；化学物質評価研究機構製）
移動相：０．１％リン酸　エタノール／水＝９０／１０
流速：１．０ｍｌ／ｍｉｎ
検出：ＵＶ検出器（２１０ｎｍ）
カラム温度：４０℃
注入量：２０μＬ
試料濃度：５％エタノール溶液
実施例１
＜アミド化＞
攪拌機、温度計、還流冷却器、及び圧力計を備えた１リットル容５ツ口フラスコに、ラウリン酸　２００ｇ（分子量２００、１モル）およびジメチルアミノプロピルアミン　７１．４ｇ（分子量１０２、０．７モル）を仕込み、窒素ガスをキャピラリー管より１００ｃｃ／Ｈｒで吹き込みながら　１５０℃へ昇温した。２時間熟成後、１８０℃に昇温し、ジメチルアミノプロピルアミン　３０．１ｇ（分子量１０２、０．３モル）を１時間かけて滴下した。その後、この条件下で２時間保持し、酸価（ＡＶ）を測定して１０以下であることを確認した後に５０℃まで冷却し、Ｎ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンを取り出した。
【００３２】
＜両性化＞
上記アミド化で得られたＮ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンを、攪拌機、温度計、還流冷却器を備えた２リットル容４ツ口フラスコに移した後に、イオン交換水　７４０ｇとモノクロロ酢酸ナトリウム　１１６．５ｇを仕込み、８０℃迄加熱した。その後、系内のｐＨを４０％水酸化ナトリウム水溶液にて１０に調整した後に５時間反応し、冷却し、３５％塩酸を用いてｐＨ調整を行い、３０％のＮ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルグリシンベタインを含む反応混合物を得た。反応混合物中のジアミド含量を測定した結果、０．０１５％であった。
【００３３】
実施例２
＜アミド化＞
実施例１のアミド化と同様にして、Ｎ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンを得た。
【００３４】
＜両性化＞
攪拌機、冷却器、滴下漏斗及び温度計を備えた４ツ口フラスコに、水２８１．１ｇ、重亜硫酸ソーダ１３０．０ｇ（１．２５モル）を仕込み、７０℃まで昇温した。次にエピクロロヒドリン１１５．６ｇ（１．２５モル）を約１時間かけて滴下した。この時発熱が起こるが系内の温度を７０〜８０℃にコントロールした。滴下終了後、８０〜９０℃で約１時間熟成を行い、３−クロロ−２−ヒドロキシプロパンスルホン酸ソーダを得た。次にエタノールを５０ｇ加え、更に上記アミド化で得られたＮ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルアミン２８４ｇ（１．０モル）を加え、９０℃で熟成を始めた。熟成を開始して１時間後より、４％水酸化ナトリウム水溶液２００ｇ（０．２モル）を５時間かけて連続的に滴下した。滴下終了後、更に４時間熟成を行った。冷却後、約３０％のＮ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルアンモニオ（２−ヒドロキシ）プロパンスルホベタインを含む反応混合物を得た。反応混合物中のジアミド含量を測定した結果、０．０５３％であった。
【００３５】
比較例１
＜アミド化＞
実施例１のアミド化と同様の反応装置に、ラウリン酸　２００ｇ（分子量２００　、１モル）を仕込み、窒素ガスをキャピラリー管より　１００ｃｃ／Ｈｒで吹き込みながら　１８０℃へ昇温した。そこへ、ジメチルアミノプロピルアミン　１０２ｇ（分子量１０２、１モル）を３時間かけて滴下した。その後、この条件下で２時間保持し、酸価（ＡＶ）を測定して１０以下であることを確認した後に５０℃まで冷却し、Ｎ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンを含む反応混合物を取り出した。
【００３６】
＜両性化＞
実施例１と同様の反応装置を用い、上記のアミド化で得られたＮ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンを用いる以外は実施例１と同様の両性化反応及び処理を行い、３０％のＮ−ラウロイルアミノプロピル−Ｎ，Ｎ−ジメチルグリシンベタインを含む反応混合物を得た。反応混合物中のジアミド含量を測定した結果０．３％であった。
【００３７】
比較例２
＜アミド化＞
特開２０００−１９１６１４号の実施例と同様にしてアミドアミンを得た。
【００３８】
即ち、７３１ｋｇのココナッツ脂肪酸（ヨウ素価≦１）を反応器に入れ、５０℃で溶かし、反応器およびその内容物を窒素でパージし、１９０℃にした。３４７ｋｇのジメチルアミノプロピルアミンを浸積チューブを介して４時間かけて添加し、水を連続的に蒸発除去した。窒素流下で反応生成物の酸価が４．５ｍｇＫＯＨ／ｇ以下になるまで混合物を１９０℃に維持した。その後、混合物を１５０℃に冷却し、窒素パージ下で浸積チューブを用いて１００ｋｇの水を１時間かけて注入し、得られた混合物を１５０℃で乾燥し、水含有率を０．１％以下にした。系を６０℃に冷却し、窒素のパージを止めて、Ｎ−ココイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンを得た。
【００３９】
＜両性化＞
実施例１と同様の反応装置を用い、上記のアミド化で得られたＮ−ココイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンを用いる以外は実施例１と同様の両性化反応及び処理を行い、３０％のＮ−ココイルアミノプロピル−Ｎ，Ｎ−ジメチルグリシンベタインを含む反応混合物を得た。反応混合物中のジアミド含量を測定した結果０．５４％であった。
【００４０】
実施例３
攪拌機、温度計、還流冷却器及び圧力計を備えた５リットル容４ツ口フラスコに、ステアリン酸　２５００ｇ（分子量２８３、８．８３モル）およびジメチルアミノプロピルアミン　８１３ｇ（分子量１０２、７．９７モル）を仕込み、窒素ガスをキャピラリー管より　４００ｃｃ／Ｈｒで吹き込みながら　１５０℃へ昇温した。１５０℃で１．５時間熟成後、１７０℃に昇温し、ジメチルアミノプロピルアミン　４５１ｇ（分子量１０２、４．４２モル）を１．５時間かけて添加した。その後、１８０℃に昇温した後に５時間熟成を行った。酸価（ＡＶ）を測定して２以下であることを確認し、過剰のジメチルアミノプロピルアミンを減圧下（２．０　ｋＰａ）除去した後、８０℃まで冷却し、Ｎ−ステアロイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンを取り出した。このアミン中のジアミド含量を測定した結果、０．０１３％であった。
【００４１】
処方例
実施例３で得られたＮ−ステアロイルアミノプロピル−Ｎ，Ｎ−ジメチルアミン（以下、実施例３のアミドアミンという）を用いて、以下に示す組成の柔軟剤組成物を、以下に示す方法で調製した。得られた柔軟剤組成物は透明であり、−５℃で２０日間保存後も透明で濁りは見られず、保存安定性が良好であった。
【００４２】
＜柔軟剤組成物の組成＞
実施例３のアミドアミン　　　　　　　　　　　　　　　８．０％
Ｃ２４ゲルベアルキル硫酸ナトリウム　　　　　　　　　５．５％
ジ（ヤシ油アルキル）ジメチルアンモニウムクロリド　１１．０％
流動パラフィン（ＲＵＤＯＬ：島貿易（株）製）　　　　１．０％
Ｃ２４ゲルベアルコール　　　　　　　　　　　　　　　１．５％
フェノキシエタノール　　　　　　　　　　　　　　　２０．０％
エタノール　　　　　　　　　　　　　　　　　　　　　２．０％
ラウリルアルコールエチレンオキシド２０モル付加物　　３．５％
塩化マグネシウム　　　　　　　　　　　　　　　　　　０．３％
香料　　　　　　　　　　　　　　　　　　　　　　　　０．４％
ＥＤＴＡ・４Ｎａ　　　　　　　　　　　　　　　　　　０．０１％
クエン酸　　　　　　　　　　　　　　　　　　　　　　０．５％
水　　　　　　　　　　　　　　　　　　　　　　　　　バランス
（塩酸でｐＨ４．６に調整）
＜柔軟剤組成物の製造法＞
所要量のフェノキシエタノール、塩化マグネシウム、エタノール、ラウリルアルコールエチレンオキシド２０モル付加物及び流動パラフィンを溶解、分散させた。次に撹拌しながら所要量の実施例３のアミドアミン、Ｃ２４ゲルベアルキル硫酸ナトリウム、ジ（ヤシ油アルキル）ジメチルアンモニウムクロリド及びＣ２４ゲルベアルコールを添加し、均一に溶解・分散するまで撹拌を続けた後、酸剤のクエン酸を所要量添加し、更に１０分撹拌後、液温を５０℃まで冷却した。次に、香料、ＥＤＴＡ・４Ｎａ、及び出来上がり重量にするのに必要な量のイオン交換水を添加して１０分間攪拌した後、塩酸を用いてｐＨを４．６に調整し、５℃の水の入ったウォーターバスにビーカーを移し、撹拌しながら３０℃に冷却した。
【００４３】
【発明の効果】
本発明の方法により、ジアミド含量が少ないアミドアミン及びアミド基含有界面活性剤を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing an amidoamine and an amide group-containing surfactant having a low diamide content.
[0002]
[Prior art]
Amide group-containing surfactants such as amidoalkyl betaines, quaternary salts or acid salts of amidoalkylamines, amidoalkylamine oxides, and amidoalkylhydroxylsulfobetaines are known in the art. It is obtained by ampholytic, quaternary, or oxidizing amidoamine obtained by a chemical reaction.
[0003]
As the alkyl source used in the production of amidoamine, oil, fatty acid lower alkyl esters such as fatty acid methyl ester, fatty acids, etc. are used. In the reaction using oil such as coconut oil, palm kernel oil, etc. Glycerin remains, and the color and odor are poor. On the other hand, the reaction using a fatty acid lower alkyl ester has a disadvantage that the cost is higher due to the higher price of the fatty acid lower alkyl ester. Therefore, using fatty acids as an alkyl source is a superior manufacturing method in quality / cost.
[0004]
As a method of using a fatty acid as an alkyl source, for example, there is a method disclosed in Patent Document 1. In this method, since the boiling point of diamine (dimethylaminopropylamine) is lower than the reaction temperature, to prevent the diamine from distilling out of the system, the fatty acid is charged first, and then the temperature is raised and the diamine is gradually added. ing. However, in this method, since the diamine is present in an excess of the fatty acid, the acid condition is reached, the bond between nitrogen and carbon in the diamine is cleaved, and the structure represented by the following general formula (VIII) or (IX) is obtained. Diamide was found to be present.
[0005]
Embedded image

[0006]
(In the formula, R represents a fatty acid residue such as coconut oil fatty acid.)
When such a diamide is present, not only does the content of the active ingredient decrease, but also a secondary amine is generated by hydrolysis of the tertiary amide group in the diamide, and the diamide becomes a turbid substance during storage at low temperature. There is a problem of precipitation.
[0007]
Amidoamine is specifically useful as a softener base, but when the above-mentioned diamide is present in a large amount, there is a problem that cloudiness occurs when the softener composition is stored at a low temperature.
[0008]
Patent Literature 2 describes reacting N, N-dimethyl-1,3-propanediamine with a fatty acid or a fatty acid fraction at 140 to 200 ° C. In a relatively high temperature reaction (170 to 200 ° C.), a large amount of amine is distilled out of the system together with generated water, and the reaction does not proceed sufficiently. As a method for carrying out the reaction at a low temperature, as described in Patent Literature 3, a method of charging an excess of amine and fatty acid and gradually increasing the temperature is employed. However, even at a relatively low temperature (140 to 160 ° C.), distillation of the amine out of the system is inevitable, and the reaction time is long and inefficient.
[0009]
[Patent Document 1]
JP 2000-191614 A [Patent Document 2]
US Patent No. 3,225,074 [Patent Document 3]
International Publication No. 98/47860 Pamphlet [0010]
[Problems to be solved by the invention]
An object of the present invention is to provide an efficient method for producing an amidoamine and an amide group-containing surfactant having a low diamide content and a low turbidity.
[0011]
[Means for Solving the Problems]
The present inventors have found that by reacting a fatty acid and a diamine in two steps, it is possible to suppress the formation of diamide during the amidation and to suppress the distillation of the amine out of the system.
[0012]
The present invention is a method for producing an amidoamine by reacting a fatty acid with a diamine, wherein the fatty acid is reacted at a temperature of 130 to 170 ° C. with 0.3 to 0.9 mole times of the diamine per mole of the fatty acid. Thereafter, the remaining diamine is further reacted at a higher temperature by 10 to 50 ° C. to produce an amidoamine, and an amidoamine obtained is amphoteric, quaternized or oxidized to produce an amide group-containing surfactant. provide.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Examples of the fatty acid used in the present invention include a fatty acid represented by the general formula (I).
[0014]
R ¹ COOH (I)
(In the formula, R ¹ represents a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 7 to 23 carbon atoms.)
Specifically, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid and coconut oil fatty acids, cottonseed oil fatty acids, corn oil fatty acids, Vegetable or animal oil fatty acids such as tallow fatty acid, babas oil fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and whale oil fatty acid. Among these, those in which R ¹ is a straight-chain alkyl group having 9 to 19 carbon atoms are preferable, and those having a straight-chain alkyl group having 9 to 17 carbon atoms are more preferable.
[0015]
As the diamine used in the present invention, a diamine represented by the general formula (II) is preferable.
[0016]
Embedded image

[0017]
(In the formula, R ² represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, and R ³ may be substituted with at least one selected from a hetero atom or a carbonyl group. A good alkyl group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ may be the same or different and represent a linear or branched alkyl group having 1 to 6 carbon atoms.)
Examples of the diamine represented by the general formula (II) include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, and diethylaminoethylamine, and dimethylaminopropylamine is preferable.
[0018]
Further, as the diamine, a diamine having a small amount of by-products contained therein (for example, a compound in which R ⁴ and / or R ⁵ is replaced by a hydrogen atom in the general formula (II)) is used, It is preferable from the viewpoint of suppressing the generation of phenol.
[0019]
In the present invention, first, a fatty acid and a diamine in an amount of 0.3 to 0.9 mole times, preferably 0.4 to 0.8 mole times based on 1 mole of the fatty acid are added at 130 to 170 ° C, preferably 140 to 160 ° C. After the reaction, the remaining diamine is further reacted at a temperature higher by 10 to 50C, preferably 10 to 30C. The remaining diamine may be added and reacted at once, or may be gradually added and reacted. The molar ratio of the total fatty acid to diamine in this reaction is preferably fatty acid: diamine = 1: 1 to 1: 2, more preferably 1: 1 to 1: 1.5.
[0020]
By the amidation reaction of the present invention as described above, an amidoamine having a low diamide content can be produced.
[0021]
As the amidoamine obtained by the production method of the present invention, a compound represented by the general formula (III) is preferable.
[0022]
Embedded image

[0023]
(Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.)
The amidoamine obtained in the present invention can be further subjected to a reaction such as amphoteric, quaternization, or oxidation by a conventionally known method to produce an amide group-containing surfactant having a low diamide content.
[0024]
Examples of such an amide group-containing surfactant include compounds represented by general formulas (IV), (V), (VI) and (VII), and represented by general formula (IV) or (V). Betaine is preferred.
[0025]
Embedded image

[0026]
(Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the above-mentioned meanings, R ⁶ is a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁷ is a 1 to 4 carbon atom. 6 represents a straight-chain or branched-chain alkyl group or hydroxyalkyl group, and X ⁻ represents an anion such as a halogen ion or an alkyl sulfate ion.)
In the present invention, the amidoamine can be amphoteric by a known method. For example, the amidoamine represented by the general formula (III) obtained by the amidation reaction as described above is replaced with the general formula (X)
YR ⁶ COOZ (X)
(In the formula, Y represents a halogen atom, Z represents a hydrogen atom or an alkali metal, and R ⁶ has the above-mentioned meaning.)
Is reacted with a monohaloalkylcarboxylic acid or a salt thereof, or 3-chloro-2-hydroxypropylsulfonic acid or a salt thereof, so that the compound is represented by the general formula (IV) or (V) having a small diamide content. Betaine can be obtained.
[0027]
Examples of the monohaloalkylcarboxylic acid represented by the general formula (X) or a salt thereof include monochloroacetic acid, monobromoacetic acid, monochloropropionic acid, monobromopropionic acid, and sodium and potassium salts thereof. Its salts are preferred. The amount of the monohaloalkylcarboxylic acid or a salt thereof or the amount of 3-chloro-2-hydroxypropylsulfonic acid or a salt thereof with respect to the amidoamine is preferably 1 to 3 times by mole, more preferably 1 to 1.15 times by mole.
[0028]
In the present invention, the addition reaction between amidoamine and a monohaloalkylcarboxylic acid represented by the general formula (X) or a salt thereof, or 3-chloro-2-hydroxypropylsulfonic acid or a salt thereof is carried out by, for example, an amidoamine and a monohaloalkylcarboxylic acid. The acid or a salt thereof is reacted at pH 8 to 10 until the betaine formation is completed, and thereafter at pH 11.5 to 13 to promote hydrolysis of the remaining monohaloalkylcarboxylate. The reaction temperature is preferably in the range of 50 to 100 ° C. The reaction may be carried out under normal pressure or under pressure.
[0029]
In the present invention, quaternization and oxidation of amidoamine can be carried out by a conventionally known method. For example, the amide amine represented by the general formula (III) obtained by the amidation reaction as described above is reacted with a quaternizing agent such as methyl chloride or dimethyl sulfate to obtain a compound of the general formula (VI) having a low diamide content. A quaternary ammonium salt represented by the general formula (III) can be obtained, and the amidoamine represented by the general formula (III) is oxidized with hydrogen peroxide, peroxysulfuric acid, Fenton's reagent, or the like, so that the diamide content is low. The amine oxide represented by (VII) can be obtained.
[0030]
【Example】
The percentages in the examples are on a weight basis unless otherwise specified. In the following examples, the diamide content was quantified by the absolute calibration curve method using a diamide with a known content as a standard under the following HPLC conditions.
[0031]
<HPLC conditions>
Column: L-COLUMN ODS (4.6 mmφ × 150 mm, 5 μm; manufactured by Chemicals Evaluation and Research Institute)
Mobile phase: 0.1% phosphoric acid ethanol / water = 90/10
Flow rate: 1.0 ml / min
Detection: UV detector (210 nm)
Column temperature: 40 ° C
Injection volume: 20 μL
Sample concentration: 5% ethanol solution Example 1
<Amidation>
In a 1-liter five-necked flask equipped with a stirrer, thermometer, reflux condenser, and pressure gauge, 200 g of lauric acid (molecular weight: 200, 1 mol) and 71.4 g of dimethylaminopropylamine (molecular weight: 102, 0.7 mol) ), And the temperature was raised to 150 ° C. while blowing nitrogen gas through the capillary tube at 100 cc / Hr. After aging for 2 hours, the temperature was raised to 180 ° C., and 30.1 g (molecular weight: 102, 0.3 mol) of dimethylaminopropylamine was added dropwise over 1 hour. Thereafter, the mixture was kept under these conditions for 2 hours, and after confirming that the acid value (AV) was 10 or less, the mixture was cooled to 50 ° C., and N-lauroylaminopropyl-N, N-dimethylamine was taken out. .
[0032]
<Amphoteric>
The N-lauroylaminopropyl-N, N-dimethylamine obtained by the above amidation was transferred to a two-liter four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. 116.5 g of sodium acetate was charged and heated to 80 ° C. Thereafter, the pH in the system was adjusted to 10 with a 40% aqueous sodium hydroxide solution, followed by a reaction for 5 hours, followed by cooling, pH adjustment using 35% hydrochloric acid, and 30% N-lauroylaminopropyl-N, A reaction mixture containing N-dimethylglycine betaine was obtained. As a result of measuring the diamide content in the reaction mixture, it was 0.015%.
[0033]
Example 2
<Amidation>
N-lauroylaminopropyl-N, N-dimethylamine was obtained in the same manner as in the amidation of Example 1.
[0034]
<Amphoteric>
281.1 g of water and 130.0 g (1.25 mol) of sodium bisulfite were charged into a four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, and the temperature was raised to 70 ° C. Next, 115.6 g (1.25 mol) of epichlorohydrin was added dropwise over about 1 hour. At this time, heat was generated, but the temperature in the system was controlled at 70 to 80 ° C. After completion of the dropwise addition, the mixture was aged at 80 to 90 ° C. for about 1 hour to obtain sodium 3-chloro-2-hydroxypropanesulfonate. Next, 50 g of ethanol was added, and 284 g (1.0 mol) of N-lauroylaminopropyl-N, N-dimethylamine obtained by the above amidation was added, and ripening was started at 90 ° C. One hour after the start of aging, 200 g (0.2 mol) of a 4% aqueous sodium hydroxide solution was continuously added dropwise over 5 hours. After completion of the dropping, aging was further performed for 4 hours. After cooling, a reaction mixture containing about 30% of N-lauroylaminopropyl-N, N-dimethylammonio (2-hydroxy) propanesulfobetaine was obtained. As a result of measuring the diamide content in the reaction mixture, it was 0.053%.
[0035]
Comparative Example 1
<Amidation>
200 g of lauric acid (molecular weight: 200, 1 mol) was charged into the same reactor as in the amidation of Example 1, and the temperature was raised to 180 ° C. while blowing nitrogen gas at 100 cc / Hr from a capillary tube. There, 102 g (molecular weight: 102, 1 mol) of dimethylaminopropylamine was added dropwise over 3 hours. Thereafter, the mixture was kept under these conditions for 2 hours, and after confirming that the acid value (AV) was 10 or less, it was cooled to 50 ° C., and the reaction containing N-lauroylaminopropyl-N, N-dimethylamine was performed. The mixture was removed.
[0036]
<Amphoteric>
Using the same reaction apparatus as in Example 1, the same amphoteric reaction and treatment as in Example 1 were carried out except that N-lauroylaminopropyl-N, N-dimethylamine obtained by the above amidation was used. % Of N-lauroylaminopropyl-N, N-dimethylglycine betaine. The diamide content in the reaction mixture was measured and found to be 0.3%.
[0037]
Comparative Example 2
<Amidation>
Amidoamine was obtained in the same manner as in the example of JP-A-2000-191614.
[0038]
That is, 731 kg of coconut fatty acid (iodine value ≦ 1) was placed in a reactor, melted at 50 ° C., and the reactor and its contents were purged with nitrogen and brought to 190 ° C. 347 kg of dimethylaminopropylamine were added via a dip tube over 4 hours and the water was continuously evaporated off. The mixture was maintained at 190 ° C. under a stream of nitrogen until the acid value of the reaction product was below 4.5 mg KOH / g. Thereafter, the mixture is cooled to 150 ° C., 100 kg of water are injected over a period of 1 hour using a dip tube under a nitrogen purge, and the resulting mixture is dried at 150 ° C. to reduce the water content to 0.1%. I did it below. The system was cooled to 60 ° C. and the nitrogen purge was turned off to give N-cocoylaminopropyl-N, N-dimethylamine.
[0039]
<Amphoteric>
Using the same reaction apparatus as in Example 1, the same amphoteric reaction and treatment as in Example 1 were carried out except that N-cocoylaminopropyl-N, N-dimethylamine obtained by the above amidation was used. % Of N-cocoylaminopropyl-N, N-dimethylglycine betaine. The diamide content in the reaction mixture was measured and found to be 0.54%.
[0040]
Example 3
In a 5-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and pressure gauge, stearic acid 2500 g (molecular weight: 283, 8.83 mol) and dimethylaminopropylamine 813 g (molecular weight: 102, 7.97 mol) , And the temperature was raised to 150 ° C. while blowing nitrogen gas at 400 cc / Hr from a capillary tube. After aging at 150 ° C. for 1.5 hours, the temperature was raised to 170 ° C., and 451 g (molecular weight: 102, 4.42 mol) of dimethylaminopropylamine was added over 1.5 hours. Thereafter, the temperature was raised to 180 ° C. and then aging was performed for 5 hours. The acid value (AV) was measured and confirmed to be 2 or less. After removing excess dimethylaminopropylamine under reduced pressure (2.0 kPa), the solution was cooled to 80 ° C., and N-stearoylaminopropyl-N , N-dimethylamine was removed. As a result of measuring the diamide content in this amine, it was 0.013%.
[0041]
Formulation Example Using N-stearoylaminopropyl-N, N-dimethylamine (hereinafter referred to as amidoamine of Example 3) obtained in Example 3, a softener composition having the following composition was prepared by the following method. Prepared. The obtained softener composition was transparent, transparent and turbid even after storage at -5 ° C for 20 days, and had good storage stability.
[0042]
<Composition of softener composition>
Amidoamine of Example 3 8.0%
C24 Sodium Guerbet alkyl sulfate 5.5%
Di (coconut oil alkyl) dimethylammonium chloride 11.0%
Liquid paraffin (RUDOL: manufactured by Shima Trading Co., Ltd.) 1.0%
C24 Guerbet alcohol 1.5%
Phenoxyethanol 20.0%
2.0% ethanol
Lauryl alcohol ethylene oxide 20 mol adduct 3.5%
Magnesium chloride 0.3%
Spice 0.4%
EDTA / 4Na 0.01%
0.5% citric acid
Water balance (adjusted to pH 4.6 with hydrochloric acid)
<Method for producing softener composition>
The required amounts of phenoxyethanol, magnesium chloride, ethanol, lauryl alcohol ethylene oxide 20 mol adduct and liquid paraffin were dissolved and dispersed. Next, the required amounts of the amidoamine of Example 3, sodium C24 Guerbet alkyl sulfate, di (coconut oil alkyl) dimethylammonium chloride and C24 Guerbet alcohol were added while stirring, and stirring was continued until the mixture was uniformly dissolved and dispersed. The required amount of an acid agent, citric acid, was added, and the mixture was further stirred for 10 minutes, and then cooled to 50 ° C. Next, flavor, EDTA-4Na, and ion-exchanged water necessary for obtaining the final weight were added, and the mixture was stirred for 10 minutes. Then, the pH was adjusted to 4.6 with hydrochloric acid, and the water was added at 5 ° C. The beaker was transferred to a water bath containing, and cooled to 30 ° C with stirring.
[0043]
【The invention's effect】
According to the method of the present invention, an amidoamine and an amide group-containing surfactant having a low diamide content can be obtained.

Claims (7)

A method for producing an amidoamine by reacting a fatty acid with a diamine, wherein the fatty acid is reacted with a diamine in an amount of 0.3 to 0.9 mole times based on 1 mole of the fatty acid at a temperature of 130 to 170 ° C., and further reacted for 10 minutes. A method for producing amidoamine, wherein the remaining diamine is reacted at a temperature higher by ５０50 ° C. The method according to claim 1, wherein the fatty acid is a fatty acid represented by the general formula (I).
R ¹ COOH (I)
(In the formula, R ¹ represents a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 7 to 23 carbon atoms.) 3. The method according to claim 1, wherein the diamine is a diamine represented by the general formula (II).

(In the formula, R ² represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, and R ³ may be substituted with at least one selected from a hetero atom or a carbonyl group. A good alkyl group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ may be the same or different and represent a linear or branched alkyl group having 1 to 6 carbon atoms.) The method according to claim 3, wherein the diamine is dimethylaminopropylamine. The method according to any one of claims 1 to 4, wherein the amidoamine is a compound represented by the general formula (III).

(Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.) A method for producing an amide group-containing surfactant, wherein the amidoamine obtained by the production method according to claim 1 is amphoteric, quaternized, or oxidized. The method according to claim 6, wherein the amide group-containing surfactant is betaine represented by the general formula (IV) or (V).

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the above-mentioned meanings, and R ⁶ represents a linear or branched alkylene group having 1 to 4 carbon atoms.)