JP3565608B2 - Carboxyl group-containing polyoxyalkylene compound - Google Patents

Description

［ただし、Ｚは２〜８個の水酸基を持つ化合物の残基、Ａ¹Ｏ、Ａ²Ｏは炭素数２〜４のオキシアルキレン基の１種または２種以上の混合物で、Ｂ¹Ｏ、Ｂ²Ｏは式（２）で示される基の１種または２種以上の混合物であり、
【化９】

（ただし、Ｒ¹は炭素数２〜５の不飽和炭化水素基である）
Ｃ¹Ｏ、Ｃ²Ｏは式（３）で示される基の１種または２種以上の混合物、
【化１０】

（ただし、Ｒ²は水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、アルキルアンモニウムまたは炭素数１〜２４の炭化水素基で同一でも異なっていてもよく、Ｒ³は炭素数２〜５のアルキレン基、Ｒ⁴は炭素数１〜１０の２価の炭化水素基または−ＣＨ（ＣＨ₂ＣＯＯＨ）−である。）
Ｃ ¹ ＯがＡ ¹ ＯまたはＢ ¹ Ｏの一部もしくは全部とランダム状に付加し、およびＣ ² ＯがＡ ² ＯまたはＢ ² Ｏの一部もしくは全部とランダム状に付加している、Ｒは炭素数１〜２４の炭化水素基またはアシル基、ｍは０〜８の整数、ｎは０〜８の整数、ｍ＋ｎ＝２〜８、０≦ａ、０≦ｂ、０≦ｉ、０≦ｊ、０≦ｐ、０≦ｑ、かつ、ａｍ＋ｂｎ＝１〜１５００、ｉｍ＋ｊｎ＝０〜１００、ｐｍ＋ｑｎ＝２〜１００を満足する。］
【０００５】
式（１）において、Ｚを残基とする２〜８個の水酸基をもつ化合物としては、エチレングリコール、プロピレングリコール、ブチレングリコール、ドデシレングリコール、オクタデシレングリコール、ネオペンチルグリコール、グリセリン、ジグリセリン、ポリグリセリン、トリメチロールエタン、トリメチロールプロパン、１，３，５ーペンタントリオール、エリスリトール、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、ソルビタン、ソルバイド、ソルビトールーグリセリン縮合物、アドニトール、アラビトール、キシリトール、マンニトールなどの多価アルコール；キシロース、アラビノース、リボース、ラムノース、グルコース、フルクトース、ガラクトース、マンノース、ソルボース、セロビオース、マルトース、イソマルトース、トレハロース、シュークロース、ラフィノース、ゲンチアノース、メレジトースなどの糖類；さらにそれらの部分エーテル化物や部分エステル化物；カテコール、レゾルシン、ハイドロキノン、フロログルシン等の多価フェノール；スチレングリコールなどの芳香族系アルコ−ル等があげられる。
【０００６】
Ａ¹Ｏ、Ａ²Ｏで示されるオキシアルキレン基としては、オキシエチレン基、オキシプロピレン基、オキトリシメチレン基、オキシブチレン基、オキシテトラメチレン基等が挙げられる。
式（２）においてＲ¹で示される炭素数２〜５の不飽和炭化水素基としては、ビニル基、アリル基、メタリル基、１，１−ジメチル−２−プロペニル基、３−メチル−３−ブテニル基などの重合性不飽和結合を有するものがある。
Ｒで示される炭素数１〜２４のアルキル基としてはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘプチル基、２−エチルヘキシル基、オクチル基、イソノニル基、デシル基、ドデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、イソセチル基、オクタデシル基、イソステアリル基、オクチルドデシル基、ドコシル基、デシルテトラデシル基、ベンジル基、クレジル基、ブチルフェニル基、ジブチルフェニル基、オクチルフェニル基、ノニルフェニル基、ドデシルフェニル基、ジオクチルフェニル基、ジノニルフェニル基、スチレン化フェニル基等があり、また更に、Ｒで示される炭素数１〜２４のアシル基としては、酢酸、プロピオン酸、酪酸、イソ酪酸、カプリル酸、２ーエチルヘキサン酸、イソノナン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、イソパルミチン酸、ステアリン酸、イソステアリン酸、アラキン酸、ベヘン酸、パルミトレイン酸、安息香酸、ヒドロキシ安息香酸、桂皮酸、没食子酸等に由来するアシル基がある。
【０００７】
更に、Ｒ²で示される炭素数１〜２４の炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘプチル基、２ーエチルヘキシル基、オクチル基、イソノニル基、デシル基、ドデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、イソセチル基、オクタデシル基、イソステアリル基、オクチルドデシル基、ドコシル基、デシルテトラデシル基、ベンジル基、クレジル基、ブチルフェニル基、ジブチルフェニル基、オクチルフェニル基、ノニルフェニル基、ドデシルフェニル基、ジオクチルフェニル基、ジノニルフェニル基、スチレン化フェニル基等がある。
また、Ｒ²で示されるアルカリ金属、アルカリ土類金属、アンモニウムまたはアルキルアンモニウムとしては、リチウム、ナトリウム、カリウム、ルビジウムなどのアルカリ金属；マグネシウム、カルシウムなどのアルカリ土類金属；アンモニウム、エチルアミン塩、プロピルアミン塩、ブチルアミン塩、ペンチルアミン塩、ヘキシルアミン塩、オクチルアミン塩、２−エチルヘキシルアミン塩、デシルアミン塩、ドデシルアミン塩、イソトリデシルアミン塩、テトラデシルアミン塩、ヘキサデシルアミン塩、イソヘキサデシルアミン塩、オクタデシルアミン塩、イソオクタデシルアミン塩、オクチルドデシルアミン塩、ドコシルアミン塩、デシルテトラデシルアミン塩、オレイルアミン塩、リノールアミン塩、ジメチルアミン塩、トリメチルアミン塩、アニリン塩などの脂肪族や芳香族のモノアミン塩；エチレンジアミン塩、テトラメチレンジアミン塩、ドデシル−プロピレンジアミン塩、テトラデシル−プロピレンジアミン塩、オクタデシル−プロピレンジアミン塩、オレイル−プロピレンジアミン塩、ジエチレットリアミン塩、トリエチレンテトラミン塩、テトラエチレンペンタミン塩、ペンタエチレンヘキサミン塩などのポリアミン塩；モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩、モノイソプロパノールアミン塩、ジイソプロパノールアミン塩、トリイソプロパノールアミン塩、これらのアルキレンオキシド付加物の塩などのアルカノールアミン塩；リジン塩、アルギニン塩などのアミノ酸塩がある。これらのうち、特に、水素原子、アルカリ金属、アルカノールアミン塩が好ましい。
【０００８】
本発明の化合物は、式（４）の化合物と式（５）の化合物を溶媒の存在下あるいは無溶剤で反応させることにより得ることができる。
【化１１】

（ただし、Ｚは２〜８個の水酸基を持つ化合物の残基、Ａ¹Ｏ、Ａ²Ｏは炭素数２〜４のオキシアルキレン基の１種または２種以上の混合物で、Ｂ¹Ｏ、Ｂ²Ｏは式（２）で示される基の１種または２種以上の混合物である。
【化１２】

（ただし、Ｒ¹は炭素数２〜５の不飽和炭化水素基である。）
Ａ ¹ ＯおよびＡ ² ＯとＢ ¹ ＯおよびＢ ² Ｏの一部もしくは全部がランダム状に付加している、Ｒ¹は炭素数１〜２４の炭化水素基またはアシル基、ｍは０〜８の整数、ｎは０〜８の整数、ｍ＋ｎ＝２〜８、０≦ａ、０≦ｂ、０≦ｐ＋ｉ、０≦ｑ、ａｍ＋ｂｎ＝１〜１５００、ｉｍ＋ｊｎ＝０〜１００、ｐｍ＋ｑｎ＝２〜１００である。
【化１３】

（ただし、Ｒ²は水素、アルカリ金属、アルカリ土類金属、アンモニウム、有機アンモニウムまたは炭素数１〜２４の炭化水素基で同一でも異なっていてもよく、Ｒ⁴は炭素数１〜１０の２価の炭化水素基または−ＣＨ（ＣＨ₂ＣＯＯＨ）−である。）
【０００９】
本発明の化合物を製造する際に、式（４）の化合物と式（５）の化合物との反応比は任意の割合が可能であり、式（４）のｉ＋ｐ、ｊ＋ｑにより不飽和基数が変化するため特定できないが、好ましくは式（４）の化合物のアルケニル基を基準とした当量数あたり、式（５）の化合物のモル比が０．１〜１００の範囲であり、特に好ましくは０．４〜１０の範囲である。
【００１０】
式（５）の化合物のモル比が０．１未満の場合には、目的とするカルボキシル基の含有率が低下し、１００を越えると未反応のカルボキシルチオール化合物が過剰に存在するようになるので精製が困難になり好ましくない。また、式（４）の化合物の分子量およびｐ、ｑ、および式（５）の化合物の仕込みモル比を調節することにより、得られる反応生成物の分子量およびカルボキシル基の数を調節することができる。すなわち、式（４）の分子量を小さくし、アルケニル基の数を多くし、式（５）の化合物の仕込み比を多くすれば分子量の小さいカルボキシル基含有率の高い反応生成物が得られ、式（４）の分子量を高くし、アルケニル基の数を少なくし、式（５）の化合物の仕込み比を少なくすれば、分子量の高いカルボキシル基含有率の低い反応生成物が得られ、式（４）の分子量を小さくし、アルケニル基の数を少なくし、式（５）の化合物の仕込み比を少なくすれば分子量の小さいカルボキシル基含有率の低い反応生成物が得られ、式（４）の分子量を高くし、アルケニル基の数を多くし、式（５）の化合物の仕込み比を多くすれば分子量の高いカルボキシル基含有率の高い反応生成物が得られる。
【００１１】
式（４）の化合物は２〜８の水酸基を持つ化合物に、水酸化カリウム、水酸化ナトリウムあるいはナトリウムメチラートなどのアルカリ触媒、あるいは三フッ化硼素、四塩化錫などのルイス酸触媒を用いて、アルキレンオキシドおよびアリルグリシジルエーテルなどのアルケニルグリシジルエーテルの一部または全部をランダム状に付加重合させることにより得ることができる。このとき、アルキレンオキシドとアルケニルグリシジルエーテルとの混合比を調節することにより、式（４）のアルケニル基の数を調節することができる。
式（４）で示される化合物中には、式（５）の化合物と反応するために少なくとも２つのＲ1が必要である。式（４）の化合物のＲ¹の炭素数は、式（５）の化合物との反応性に関係があり、長すぎると反応性に乏しくなるので炭素数２〜５が適当である。
Ｒ³は、式（４）においてＲ¹で示される炭素数２〜５の不飽和炭化水素基としての具体例のビニル基、アリル基、メタリル基、１，１−ジメチル−２−プロペニル基、３−メチル−３−ブテニル基などの重合性不飽和結合と式（５）の化合物との反応に由来する基であり、具体的には、−ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₂−があげられる。好ましくは、アリル基、メタリル基より由来する−ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ（ＣＨ₃）ＣＨ₂−である。
Ｒ⁴は炭素数１〜１０の２価の炭化水素基または−ＣＨ（ＣＨ₂ＣＯＯＨ）−で、炭素数１〜１０の２価の炭化水素基としては、−ＣＨ₂−、−Ｃ₂Ｈ₄−、−ＣＨ（ＣＨ₃）−、−Ｃ₃Ｈ₆−、−Ｃ₆Ｈ₄−、−Ｃ₆Ｈ₄Ｃ₂Ｈ₄−などが挙げられる。
【００１２】
Ａ¹Ｏ、Ａ²Ｏの炭素数は２〜４の範囲で任意に選択できるが、Ｒ¹との組み合わせで、親水性にも油溶性にもすることができる。Ａ¹Ｏ、Ａ²Ｏがオキシエチレン基のみの場合や、混合物の場合でもオキシエチレン基が２５モル％以上のときには親水性になり、２５モル％未満でオキシエチレン基を用いるか、他の炭素数３または４のオキシアルキレン基の場合には親油性になる。
【００１３】
式（４）の化合物と式（５）の化合物から本発明の化合物を得るための反応は常圧で行うことが可能であり、反応温度は特に限定されないが、０℃以下では反応時間が長くなり、１５０℃を越えると反応時の圧力が高くなり反応操作が煩雑になるので、０〜１５０℃の範囲、好ましくは０〜１００℃の範囲である。
また、反応時間は仕込みモル比や反応温度により異なるが、３０分〜４０時間の範囲で行うのが通常である。
【００１４】
また、反応に際して式（５）の化合物の取り扱いおよび反応をより円滑に行うために、溶媒を用いてもよい。この溶媒としては系を均一にする目的で使用するので、メタノール、エタノール、イソプロパノールなどの脂肪族アルコール系溶媒、トルエン、キシレンなどの芳香族系溶媒、ジクロロエタン、クロロホルム等のハロゲン系溶媒、アセトン、メチルエチルケトンなどのケトン系溶媒、ジメチルホルムアミド、ジメチルスルホキシドなどの極性溶媒、水などの種々の溶媒が使用できる。
これらの溶媒を使用する場合、溶媒量は反応温度、式（４）の化合物の構造、溶媒の種類により異なるので特に規定されないが、多すぎると精製に時間がかかるため、通常、式（４）の化合物と式（５）の化合物の合計量に対して、０〜５００重量％の範囲である。
【００１５】
本発明の化合物は、式（４）におけるＡ¹Ｏ、Ａ²Ｏ、Ｂ¹Ｏ、Ｂ²Ｏ、Ｒ、Ｚ、ｍ、ｎ、ｉ＋ｐ、ｊ＋ｑ、ａ、ｂ、式（５）のＲ²および式（４）のアルケニル基基準当量あたりの式（５）の化合物のモル比を適当に変化させることにより、水溶性の液体から水難溶性の固体まで得ることができ、かつ骨格中の側鎖のカルボキシル基数を任意に調節できるので、水溶性から脂溶性、液体から固体までの種々の形態の用途に使用できる。
【００１６】
【発明の効果】
本発明の化合物は骨格中の側鎖に複数のカルボキシル基を持つポリオキシアルキレン化合物であり、カルボキシル基含有率の高い高分子量の化合物を容易に得ることができ、カルボキシル基に起因した性質を顕著にしめすため、潤滑油分野の添加剤や合成樹脂用の添加剤や相溶化剤として利用することができる。また医薬用薬剤等のアミノ基や水酸基と容易に反応するため、薬物送達システムの担体としても利用できる。
また、本発明の合成方法によれば、カルボキシル基含有化合物を短時間で収率良くかつ容易に、しかも反応触媒及び特殊な装置を使用せずに１段階反応により製造することができる。
【００１７】
【実施例】
以下、本発明を実施例により更に詳細に説明する。
製造例１
ジエチレングリコール５３g（０．５モル）と水酸化ナトリウム２．０gを５リットル容オートクレーブに仕込み、系内を窒素ガスに置換した後１００℃に昇温した。ついで、エチレンオキシド１４５２ｇ（３３モル）とアリルグリシジルエーテル５９８．５ｇ（５．２５モル）を計量槽に計り取り、均一になるまで混合した。１００〜１５０℃、１０ｋｇ／ｃｍ²以下の条件で計量槽よりエチレンオキシドとアリルグリシジルエーテル混合物を８時間かけて圧入したのちさらに１時間反応を続けた。次に窒素ガスを通じながら減圧下（２００ｍｍＨｇ以下）、未反応エチレンオキシドとアリルグリシジルエーテルを除去しながら６０℃まで冷却した。その後、１０％塩酸水溶液でｐＨを７．０に調整し、１００℃、１００ｍｍＨｇ以下で１時間脱水を行った。次に、８０℃に冷却して析出した塩をろ別して化合物１９８６ｇを得た。
得られた化合物の水酸基価は２８．２（計算値は２８．０）、不飽和度は２．４８（計算値は２．４９）であった。出発原料、反応条件、分析値より表１に示すＮｏ．１の化合物と推定した。分析値を表２に示す。
【００１８】
【表１】

【００１９】
【表２】

【００２０】
なお、水酸基価は、ＪＩＳ Ｋ−１５５７ ６．４（１９７０）の方法に準じて行い、不飽和度は、ＪＩＳ Ｋ−１５５７ ６．７（１９７０）の方法に準じて行った。
【００２１】
得られた化合物のゲルパーミエーションクロマトグラムを図１に、赤外線吸収スペクトルを図２に、¹Ｈ−ＮＭＲスペクトルを図３に示す。
【００２２】
また、ゲルパーミエーションクロマトグラフィの測定条件は次のとおりである。
機種 ；ＳＨＯＵＤＥＸ ＧＰＣ ＳＹＳＴＥＭ−１１
展開溶媒 ；テトラヒドロフラン
サンプル ；０．１５％×１００×０．００１ｍｌ
流速 ；１．０ｍｌ／ｍｉｎ
充填カラム；ＳＨＯＤＥＸ ＫＦ−８０１、ＫＦ−８０３、ＫＦ−８０４
カラム温度；４０℃
カラム長さ；Ｉ．Ｄ ８ｍｍ×３０ｃｍ×３
検出器 ；ＲＩ×８
ゲルパーミエーションクロマトグラフィによる測定結果は次のとおりである。
数平均分子量（ＭＮ） ＝ ３９３４
重量平均分子量（ＭＷ） ＝ ４０９４
多分散度（ＭＷ）／（ＭＮ）＝１．０４２
赤外線吸収スペクトルの測定結果は次のとおりである。
１６５０ｃｍ^-1にＣ＝Ｃの吸収が認められる。
１７３０ｃｍ^-1にカルボキシル基の吸収が認められる。
¹Ｈ−ＮＭＲスペクトルの測定結果は次のとおりである。
¹Ｈ−ＮＭＲ（δ（ppm）,CDCl₃/TMS）
δ＝５．２ppm（＝ＣＨ₂）
δ＝５．９ppm（−ＣＨ＝）
【００２３】
製造例２
グリセリン９２ｇ（１モル）と水酸化ナトリウム６．０ｇを５リットル容オートクレーブに仕込み、系内を窒素ガスに置換した後１００℃に昇温した。ついで、エチレンオキシド６９３ｇ（１５．７５モル）を、１００〜１５０℃、１０ｋｇ／ｃｍ²以下の条件で４時間かけて圧入したのち、さらに１時間反応を続けた。続いて、アリルグリシジルエーテル７１８．２ｇ（６．３モル）とプロピレンオキシド１６４４．３ｇ（２８．３５モル）を計量槽に計り取り、均一になるまで混合したものを、１００〜１５０℃、１０ｋｇ／ｃｍ²以下の条件で計量槽より８時間かけて圧入したのちさらに１時間反応を続けた。次に窒素ガスを通じながら減圧下（２００ｍｍＨｇ以下）、未反応のエチレンオキシド、プロピレンオキシドおよびアリルグリシジルエーテルを除去しながら６０℃まで冷却した。その後、１０％塩酸水溶液でｐＨを７．０に調整し、１００℃、１００ｍｍＨｇ以下で１時間脱水を行った。次に、８０℃に冷却し析出した塩をろ別して化合物２９７０ｇを得た。
得られた化合物の水酸基価は５７．２（計算値は５６．１）、不飽和度は１．９８（計算値は２．０）であり、同様に表１のＮｏ．２の化合物と推定した。
【００２４】
製造例３
５リットル容オートクレーブに表１のＮｏ．２の化合物２１００g（０．７モル）、ナトリウムメチラート５９．４g（1.１モル）を採り、系内を窒素ガスに置換した後、かき混ぜながら１００℃に昇温し、１００ｍｍＨｇ以下で１時間アルコラート化を行った。次に、窒素ガスによって系内を常圧にし、ボンベより塩化メチルを吹き込み、系内が１ｋｇ／ｃｍ²になるように吹き込み管を調節しながら１００℃で７時間保持した。その後、窒素ガスを吹き込みながら６０℃まで冷却すると共に過剰の塩化メチルを留去した。その後、１０％塩酸水溶液でｐＨを７．０に調整し、１００℃、１００ｍｍＨｇ以下で１時間脱水を行った。次に、８０℃に冷却し析出した塩をろ別して１９００ｇ化合物を得た。
得られた化合物の水酸基価は１．３（計算値は０）、不飽和度は１．９５（計算値は１．９７）であった。その結果から表１のＮｏ．３の化合物とした。
【００２５】
製造例４〜７
以下、製造例１と同様の手法により、表１に示すＮｏ．４〜Ｎｏ．７の化合物を得た。分析値は表２に示す。
【００２６】
実施例１（メルカプト酢酸；ＨＳＣＨ₂ＣＯＯＨ）
４つ口フラスコに一般式（５）の化合物としてメルカプト酢酸９０２ｇ(９．８モル)を入れ、かき混ぜながら温度を３５℃±５℃に保持した。ついで表１Ｎｏ．１の一般式（４）の化合物９９５ｇ（０．２５モル）をメタノール９９５ｇに溶解させ、滴下ロートにより４つ口フラスコに５時間かけて滴下した。全量滴下終了後、さらに４０±５℃で５時間保持して反応を続けた。
次に６０±１０℃、２００mmHg以下の減圧下でメタノールを留去したのち、クロロホルム２０００ｇに再び溶解させた。次に全量を分液ロートに移し、飽和食塩水１リットルで３回水洗し未反応のメエルカプト酢酸を除去した。ついで１１０±１０℃、窒素雰囲気下、５０mmHg以下の真空下でクロロホルムおよび水を留去し、析出した食塩を濾過により除去し、表５のＮｏ．１に示す化合物９３０ｇを得た。
得られた化合物の酸価は１１２．８（計算値１１３．３）、不飽和度０．０１（計算値０）であった。反応条件、分析値、生成物の構造を表３、表４、表５に示す。なお、酸価の測定はＪＩＳ Ｋ−１５５７，６．６（１９７０）の方法に準じて行った。反応条件、分析値、生成物をそれぞれ表３、４、５に示す。
【００２７】
【表３】

【００２８】
【表４】

【００２９】
【表５】

【００３０】
また、ゲルパーミエーションクロマトグラムを図４に、赤外線吸収スペクトルを図５に、ＮＭＲスペクトルを図６に示す。
赤外線吸収スペクトルの測定結果は次のとおりである。
１６５０ｃｍ^-1のＣ＝Ｃの吸収が消失している。
¹Ｈ−ＮＭＲスペクトルの測定結果は次のとおりである。
¹Ｈ−ＮＭＲ（δ(ppm),CDCl₃/TMS）
δ＝１．８５ppm（−Ｏ−ＣＨ₂ＣＨ ₂ ＣＨ₂−Ｓ−ＣＨ₂−ＣＯＯＨ）
δ＝２．７５ppm（−Ｏ−ＣＨ₂ＣＨ₂ＣＨ ₂ −Ｓ−ＣＨ₂−ＣＯＯＨ）
δ＝３．２ ppm（−Ｏ−ＣＨ₂ＣＨ₂ＣＨ₂−Ｓ−ＣＨ ₂ −ＣＯＯＨ）
図１〜図３と図４〜図６を比較すると、メルカプト酢酸と製造例１の化合物が反応していることがわかる。
【００３１】
実施例２（３−メルカプトプロピオン酸；ＨＳＣ₂Ｈ₄ＣＯＯＨ）
４つ口フラスコに一般式（５）の化合物として３−メルカプトプロピオン酸５３０ｇ(５モル)を入れ、かき混ぜながら温度を３５℃±５℃に保持した。ついで表１Ｎｏ．２の式（４）の化合物９００ｇ（０．３モル）をメタノール５００ｇに溶解させ、滴下ロートにより４つ口フラスコに５時間かけて滴下した。全量滴下終了後、さらに４０±５℃で５時間保持し反応を続けた。
次に６０±１０℃、２００mmHg以下の減圧下でメタノールを留去したのち、クロロホルム２０００ｇに再び溶解させた。次に全量を分液ロートに移し、飽和食塩水１リットルで３回水洗して未反応の３−メルカプトプロピオン酸を除去した。ついで１１０±１０℃、窒素雰囲気下、５０mmHg以下の真空下でクロロホルムおよび水を留去し、析出した食塩を濾過により除去し、表５のＮｏ．２に示す化合物８６０ｇを得た。
得られた化合物の酸価は９２．３（計算値９１．８）、不飽和度０．０（計算値０）であった。
【００３２】
実施例３（メルカプトコハク酸＝ＨＳＣ（-Ｈ）（-ＣＯＯＨ）（-ＣＨ₂ＣＯＯＨ））
４つ口フラスコに式（５）の化合物としてメルカプトコハク酸９００ｇ(６モル)と、水９２４ｇを入れかき混ぜながら温度を３５℃±５℃に保持した。ついで表１Ｎｏ．１の式（４）の化合物９９５ｇ（０．２５モル）を水４５０ｇに溶解させ、滴下ロートにより４つ口フラスコに５時間かけて滴下した。全量滴下終了後、さらに４０±５℃で５時間保持し反応を続けた。
次に、クロロホルム２０００ｇを加え、全量を分液ロートに移し、飽和食塩水２リットルで３回水洗し未反応のメルカプトコハク酸を除去した。ついで１１０±１０℃、窒素雰囲気下、５０mmHg以下の真空下でクロロホルムおよび水を留去し、析出する食塩を濾過により除去して、表５のＮｏ．３に示す化合物１１１０ｇを得た。
得られた化合物の酸価は１９８．４（計算値２０２．８）、不飽和度０．０２（計算値０）であった。同様に結果を表に示す。
【００３３】
実施例４〜８
以下、同様に表１の原料を用い、表３に示す反応条件で表４に示す化合物の分析値から、表５に示すＮｏ．４〜Ｎｏ．７の化合物を得た。実施例１〜８より、複数のカルボキシル基を持つポリオキシアルキレン化合物が得られたことがわかる。
【００３４】
【図面の簡単な説明】
図１は製造例１の化合物のゲルパーミエーションクロマトグラムである。
図２は製造例１の化合物の赤外線吸収スペクトル図である。
図３は製造例１の化合物の¹Ｈ−ＮＭＲ（核磁気共鳴）スペクトル図である。
図４は実施例１の化合物のゲルパーミエーションクロマトグラムである。
図５は実施例１の化合物の赤外線吸収スペクトル図である。
図６は実施例１の化合物の¹Ｈ−ＮＭＲスペクトル図である。[0001]
[Industrial applications]
The present invention relates to a polyoxyalkylene compound having two or more carboxyl groups on the side chain of the polyoxyalkylene group skeleton.
[0002]
[Prior art]
Compounds in which the terminal hydroxyl group of polyoxyalkylene glycol has been substituted with a carboxyl group have been described in lubricating oils (JP-B-63-4877) or synthetic resin additives (JP-A-63-182343). It's being used. In recent years, polyoxyalkylene compounds have attracted attention as important carriers for drug delivery systems (DDS), and research has been actively conducted on compounds in which an amino group or a carboxyl group has been introduced into polyalkylene glycol. It has become. (For example, BIOCONJUGATE CHEM., 3 (4) 275-276) However, a polyoxyalkylene compound having a large number of carboxyl groups in a side chain in the skeleton of the polyoxyalkylene group is not known.
[0003]
[Problems to be solved by the invention]
The polyoxyalkylene compound having a plurality of carboxyl groups in the side chain in the skeleton has the following advantages because the carboxyl group content is higher than the molecular weight.
(1) In the field of synthetic resin additives, it is excellent in improving the compatibility effect.
(2) In the lubricating oil field, it is excellent in improving heat resistance.
(3) DDS is used in the field of medicine and biochemistry, and many drugs can be transported at one time, so it is useful as a carrier for drug delivery systems.
However, the polyoxyalkylene glycol carboxylic acids provided so far are synthesized by replacing the terminal hydroxyl group of the polyoxyalkylene glycol with a carboxyl group, so that the number of carboxyl groups that can be introduced into the skeleton is limited. Was. Further, in order to increase the carboxyl group content, the only option is to reduce the molecular weight of the polyoxyalkylene glycol. In the field of the synthetic resin additive of (1), bleeding tends to occur when added. Further, in the field of lubricating oils of (2), there is a problem that it is difficult to give a product a necessary viscosity, or there is a problem that it is too toxic due to its low molecular weight for use in DDS of (3). Was.
Therefore, a polyoxyalkylene compound containing a plurality of carboxyl groups in the side chain in the skeleton of the compound is strongly desired. The compound is considered to have improved compatibility in the field of synthetic resin additives, improved heat resistance in the field of lubricating oils, increased number of drug-bonding groups and reduced toxicity in the field of DDS.
An object of the present invention is to provide a compound having a carboxyl group on the side chain of a skeleton useful as a raw material for cosmetics, biomaterials, medicines, agricultural chemicals, or the like, or as an additive for lubricating oil or synthetic resin.
[0004]
[Means for Solving the Problems]
The present inventors can react an alkenyl ether compound having a specific structure with a carboxyl thiol compound without using a reaction catalyst and a special apparatus, and easily and in high yield from these, a plurality of carboxyl groups on the side chain. The present inventors have found that a polyoxyalkylene compound having the same can be obtained, and reached the present invention. Here, the carboxyl thiol compound refers to a compound having a carboxyl group and a thiol group in the same molecule.
The present invention is a carboxyl group-containing polyoxyalkylene compound represented by the formula (1) and a method for producing the same.
Embedded image

Wherein Z is a residue of a compound having 2 to 8 hydroxyl groups, A ¹ O and A ² O are one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms, and B ¹ O, B ² O is one or a mixture of two or more groups represented by the formula (2);
Embedded image

(However, R ¹ is an unsaturated hydrocarbon group having 2 to 5 carbon atoms)
C ¹ O and C ² O are one kind or a mixture of two or more kinds of groups represented by the formula (3);
Embedded image

(However, R ² may be the same or different from a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, alkylammonium or a hydrocarbon group having 1 to 24 carbon atoms, and R ³ may be an alkylene having 2 to 5 carbon atoms. And the group R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms or —CH (CH ₂ COOH) —.
R wherein C ¹ O is randomly added to part or all of A ¹ O or B ¹ O, and C ² O is randomly added to part or all of A ² O or B ² O ; Is a hydrocarbon group or an acyl group having 1 to 24 carbon atoms, m is an integer of 0 to 8, n is an integer of 0 to 8, m + n = 2 to 8, 0 ≦ a, 0 ≦ b, 0 ≦ i, 0 ≦ j, 0 ≦ p, 0 ≦ q, and am + bn = 1 to 1500, im + jn = 0 to 100, and pm + qn = 2 to 100 are satisfied. ]
[0005]
In the formula (1), compounds having 2 to 8 hydroxyl groups having Z as a residue include ethylene glycol, propylene glycol, butylene glycol, dodecylene glycol, octadecylene glycol, neopentyl glycol, glycerin, Glycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentanetriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbide, sorbitol-glycerin condensate, adonitol, arabitol, xylitol, mannitol Polyhydric alcohols such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltaux Saccharides such as isomaltose, trehalose, sucrose, raffinose, gentianose, and melezitose; partially etherified and partially esterified products thereof; polyhydric phenols such as catechol, resorcin, hydroquinone, and phloroglucin; aromatic alcohols such as styrene glycol And the like.
[0006]
Examples of the oxyalkylene group represented by A ¹ O and A ² O include an oxyethylene group, an oxypropylene group, an oxytricimethylene group, an oxybutylene group, and an oxytetramethylene group.
Examples of the unsaturated hydrocarbon group having 2 to 5 carbon atoms represented by R ¹ in the formula (2) include a vinyl group, an allyl group, a methallyl group, a 1,1-dimethyl-2-propenyl group, and a 3-methyl-3- group. Some have a polymerizable unsaturated bond such as a butenyl group.
Examples of the alkyl group having 1 to 24 carbon atoms represented by R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, an isoheptyl group, -Ethylhexyl group, octyl group, isononyl group, decyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, isocetyl group, octadecyl group, isostearyl group, octyldodecyl group, docosyl group, decyltetradecyl group, benzyl group, There are cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group, styrenated phenyl group, and the like. Acyl groups such as acetic acid, Pionic, butyric, isobutyric, caprylic, 2-ethylhexanoic, isononanoic, capric, lauric, myristic, palmitic, isopalmitic, stearic, isostearic, arachinic, behenic, palmitoleic, benzoic There are acyl groups derived from acids, hydroxybenzoic acid, cinnamic acid, gallic acid and the like.
[0007]
Further, the hydrocarbon group having 1 to 24 carbon atoms represented by R ² includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a hexyl group. , Isoheptyl, 2-ethylhexyl, octyl, isononyl, decyl, dodecyl, isotridecyl, tetradecyl, hexadecyl, isocetyl, octadecyl, isostearyl, octyldodecyl, docosyl, decyltetradecyl Group, benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group, and styrenated phenyl group.
Examples of the alkali metal, alkaline earth metal, ammonium or alkyl ammonium represented by R ² include alkali metals such as lithium, sodium, potassium, and rubidium; alkaline earth metals such as magnesium and calcium; ammonium, ethylamine salts, propyl Amine salts, butylamine salts, pentylamine salts, hexylamine salts, octylamine salts, 2-ethylhexylamine salts, decylamine salts, dodecylamine salts, isotridecylamine salts, tetradecylamine salts, hexadecylamine salts, isohexadecyl Amine salt, octadecylamine salt, isooctadecylamine salt, octyldodecylamine salt, docosylamine salt, decyltetradecylamine salt, oleylamine salt, linoleamine salt, dimethylamine salt, trimethyi Aliphatic or aromatic monoamine salts such as amine salts and aniline salts; ethylenediamine salts, tetramethylenediamine salts, dodecyl-propylenediamine salts, tetradecyl-propylenediamine salts, octadecyl-propylenediamine salts, oleyl-propylenediamine salts, diethylates Polyamine salts such as liamine salts, triethylenetetramine salts, tetraethylenepentamine salts, pentaethylenehexamine salts; monoethanolamine salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts, triisopropanolamine And alkanolamine salts such as salts of these alkylene oxide adducts; amino acid salts such as lysine salts and arginine salts. Among these, a hydrogen atom, an alkali metal, and an alkanolamine salt are particularly preferable.
[0008]
The compound of the present invention can be obtained by reacting the compound of the formula (4) with the compound of the formula (5) in the presence or absence of a solvent.
Embedded image

(Where Z is a residue of a compound having 2 to 8 hydroxyl groups, A ¹ O and A ² O are one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms, and B ¹ O, B ² O is one or a mixture of two or more groups represented by the formula (2).
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(However, R ¹ is an unsaturated hydrocarbon group having 2 to 5 carbon atoms.)
A ¹ O and A ² O and a part or all of B ¹ O and B ² O are randomly added, R ¹ is a hydrocarbon group or an acyl group having 1 to 24 carbon atoms, and m is 0 to 8 N is an integer of 0 to 8, m + n = 2 to 8, 0 ≦ a, 0 ≦ b, 0 ≦ p + i, 0 ≦ q, am + bn = 1 to 1500, im + jn = 0 to 100, pm + qn = 2 to 100 It is.
Embedded image

(However, R ² may be the same or different from hydrogen, an alkali metal, an alkaline earth metal, ammonium, organic ammonium or a hydrocarbon group having 1 to 24 carbon atoms, and R ⁴ may be a divalent having 1 to 10 carbon atoms.) Or —CH (CH ₂ COOH) —.)
[0009]
In producing the compound of the present invention, the reaction ratio between the compound of the formula (4) and the compound of the formula (5) can be any ratio, and the number of unsaturated groups varies depending on i + p and j + q in the formula (4). However, the molar ratio of the compound of the formula (5) is preferably in the range of 0.1 to 100, and particularly preferably 0.1 to 100, per equivalent number based on the alkenyl group of the compound of the formula (4). It is in the range of 4-10.
[0010]
When the molar ratio of the compound of the formula (5) is less than 0.1, the content of the target carboxyl group decreases, and when it exceeds 100, the unreacted carboxylthiol compound becomes excessively present. It is not preferable because purification becomes difficult. Further, by adjusting the molecular weight and p, q of the compound of the formula (4) and the charged molar ratio of the compound of the formula (5), the molecular weight and the number of carboxyl groups of the obtained reaction product can be adjusted. . That is, by decreasing the molecular weight of the formula (4), increasing the number of alkenyl groups, and increasing the charge ratio of the compound of the formula (5), a reaction product having a small molecular weight and a high carboxyl group content can be obtained. If the molecular weight of (4) is increased, the number of alkenyl groups is reduced, and the charge ratio of the compound of the formula (5) is reduced, a reaction product having a high molecular weight and a low carboxyl group content is obtained. )), The number of alkenyl groups is reduced, and the charge ratio of the compound of the formula (5) is reduced to obtain a reaction product having a small molecular weight and a low carboxyl group content. Is increased, the number of alkenyl groups is increased, and the charge ratio of the compound of the formula (5) is increased, a reaction product having a high molecular weight and a high carboxyl group content can be obtained.
[0011]
The compound of the formula (4) is prepared by adding a compound having 2 to 8 hydroxyl groups to an alkali catalyst such as potassium hydroxide, sodium hydroxide or sodium methylate or a Lewis acid catalyst such as boron trifluoride or tin tetrachloride. , An alkylene oxide and all or part of an alkenyl glycidyl ether such as an allyl glycidyl ether can be obtained by random addition polymerization. At this time, the number of alkenyl groups of the formula (4) can be adjusted by adjusting the mixing ratio between the alkylene oxide and the alkenyl glycidyl ether.
In the compound represented by the formula (4), at least two R 1 are required to react with the compound of the formula (5). The number of carbon atoms of R ^{1 in} the compound of the formula (4) is related to the reactivity with the compound of the formula (5), and if it is too long, the reactivity becomes poor.
R ³ is a vinyl group, an allyl group, a methallyl group, a 1,1-dimethyl-2-propenyl group as a specific example of a C 2-5 unsaturated hydrocarbon group represented by R ¹ in the formula (4), a group derived from the reaction of a polymerizable unsaturated bond such as 3-methyl-3-butenyl group with a compound of formula (5), _{specifically, -CH 2 CH 2 -, -} CH 2 CH 2 CH _{2 -, - CH 2 CH 2} CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 CH 2 - and the like. Preferably, -CH ₂ CH ₂ CH ₂ derived from allyl, from methallyl _{-, - CH 2 CH (CH} 3) CH 2 - is.
R ⁴ is a divalent hydrocarbon group or -CH having 1 to 10 carbon atoms (CH ₂ COOH) - and, as the divalent hydrocarbon group having 1 to 10 carbon atoms, -CH ₂ -, - C ₂ H _{4 -, - CH (CH 3} ) -, - C 3 H 6 -, - C 6 H 4 -, - C 6 H 4 C 2 H 4 - , and the like.
[0012]
The carbon number of A ¹ O and A ² O can be arbitrarily selected in the range of 2 to 4, but in combination with R ^1, it can be made hydrophilic or oil-soluble. Even when A ¹ O and A ² O are oxyethylene groups alone or in the case of a mixture, they become hydrophilic when the oxyethylene groups are 25 mol% or more, and when less than 25 mol%, oxyethylene groups are used or other carbon atoms are used. In the case of the oxyalkylene group of the formula 3 or 4, the compound becomes lipophilic.
[0013]
The reaction for obtaining the compound of the present invention from the compound of the formula (4) and the compound of the formula (5) can be carried out at normal pressure, and the reaction temperature is not particularly limited. If the temperature exceeds 150 ° C., the pressure during the reaction increases, and the reaction operation becomes complicated. Therefore, the temperature is in the range of 0 to 150 ° C., preferably in the range of 0 to 100 ° C.
The reaction time varies depending on the charged molar ratio and the reaction temperature, but is usually in the range of 30 minutes to 40 hours.
[0014]
In addition, a solvent may be used to facilitate the handling and reaction of the compound of the formula (5) during the reaction. Since this solvent is used for the purpose of homogenizing the system, aliphatic alcohol solvents such as methanol, ethanol and isopropanol, aromatic solvents such as toluene and xylene, halogen solvents such as dichloroethane and chloroform, acetone and methyl ethyl ketone Ketone solvents such as dimethylformamide and dimethyl sulfoxide, and various solvents such as water can be used.
When these solvents are used, the amount of the solvent is not particularly defined because it varies depending on the reaction temperature, the structure of the compound of the formula (4), and the type of the solvent. Is in the range of 0 to 500% by weight based on the total amount of the compound of the formula (5) and the compound of the formula (5).
[0015]
The compound of the present invention is obtained by preparing A ¹ O, A ² O, B ¹ O, B ² O, R, Z, m, n, i + p, j + q, a, b in the formula (4) and R ^{2 in the} formula (5). By appropriately changing the molar ratio of the compound of the formula (5) per equivalent of the alkenyl group of the formula (4), a water-soluble liquid to a poorly water-soluble solid can be obtained, and the side chain in the skeleton can be obtained. Can be arbitrarily adjusted, so that it can be used for various forms of use from water-soluble to fat-soluble and from liquid to solid.
[0016]
【The invention's effect】
The compound of the present invention is a polyoxyalkylene compound having a plurality of carboxyl groups on the side chain in the skeleton, and a high-molecular-weight compound having a high carboxyl group content can be easily obtained. For example, it can be used as an additive in the lubricating oil field, an additive for a synthetic resin, or a compatibilizer. Further, since it easily reacts with an amino group or a hydroxyl group of a pharmaceutical agent or the like, it can be used as a carrier of a drug delivery system.
Further, according to the synthesis method of the present invention, a carboxyl group-containing compound can be produced by a one-step reaction in a short time with good yield and without using a reaction catalyst and a special device.
[0017]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
Production Example 1
53 g (0.5 mol) of diethylene glycol and 2.0 g of sodium hydroxide were charged into a 5-liter autoclave, and the inside of the system was replaced with nitrogen gas. Next, 1452 g (33 mol) of ethylene oxide and 598.5 g (5.25 mol) of allyl glycidyl ether were measured in a measuring tank and mixed until uniform. After a mixture of ethylene oxide and allyl glycidyl ether was injected from the measuring tank at 100 to 150 ° C. and 10 kg / cm ² or less over 8 hours, the reaction was further continued for 1 hour. Next, the system was cooled to 60 ° C. while removing unreacted ethylene oxide and allyl glycidyl ether under reduced pressure (200 mmHg or less) while passing nitrogen gas. Thereafter, the pH was adjusted to 7.0 with a 10% hydrochloric acid aqueous solution, and dehydration was performed at 100 ° C. and 100 mmHg or less for 1 hour. Next, the mixture was cooled to 80 ° C., and the precipitated salt was separated by filtration to obtain 1986 g of a compound.
The hydroxyl value of the obtained compound was 28.2 (calculated value: 28.0), and the degree of unsaturation was 2.48 (calculated value: 2.49). From the starting materials, reaction conditions, and analytical values, No. One compound was estimated. The analysis values are shown in Table 2.
[0018]
[Table 1]

[0019]
[Table 2]

[0020]
The hydroxyl value was determined according to the method of JIS K-1557 6.4 (1970), and the degree of unsaturation was determined according to the method of JIS K-1557 6.7 (1970).
[0021]
The gel permeation chromatogram of the obtained compound is shown in FIG. 1, the infrared absorption spectrum is shown in FIG. 2, and the ¹ H-NMR spectrum is shown in FIG.
[0022]
The measurement conditions of the gel permeation chromatography are as follows.
Model: SHOUdex GPC SYSTEM-11
Developing solvent; tetrahydrofuran sample; 0.15% x 100 x 0.001 ml
Flow rate: 1.0 ml / min
Packed column; SHOdex KF-801, KF-803, KF-804
Column temperature; 40 ° C
Column length; D 8mm × 30cm × 3
Detector: RI × 8
The measurement results by gel permeation chromatography are as follows.
Number average molecular weight (MN) = 3934
Weight average molecular weight (MW) = 4094
Polydispersity (MW) / (MN) = 1.042
The measurement results of the infrared absorption spectrum are as follows.
At 1650 cm ^-1 , absorption of C = C is observed.
At 1730 cm ^-1 , absorption of a carboxyl group is observed.
The measurement results of the ¹ H-NMR spectrum are as follows.
¹ H-NMR (δ (ppm), CDCl ₃ / TMS)
δ = 5.2 ppm (= CH ₂ )
δ = 5.9 ppm (-CH =)
[0023]
Production Example 2
92 g (1 mol) of glycerin and 6.0 g of sodium hydroxide were charged into a 5-liter autoclave, the system was purged with nitrogen gas, and then heated to 100 ° C. Next, 693 g (15.75 mol) of ethylene oxide was injected over 4 hours under the conditions of 100 to 150 ° C. and 10 kg / cm ² or less, and the reaction was further continued for 1 hour. Subsequently, 718.2 g (6.3 mol) of allyl glycidyl ether and 1644.3 g (28.35 mol) of propylene oxide were weighed into a measuring tank, and the mixture was mixed until the mixture became uniform. After pressurizing for 8 hours from the measuring tank under the condition of cm ² or less, the reaction was further continued for 1 hour. Then, the mixture was cooled to 60 ° C. while removing unreacted ethylene oxide, propylene oxide and allyl glycidyl ether under a reduced pressure (200 mmHg or less) while passing nitrogen gas. Thereafter, the pH was adjusted to 7.0 with a 10% hydrochloric acid aqueous solution, and dehydration was performed at 100 ° C. and 100 mmHg or less for 1 hour. Next, the mixture was cooled to 80 ° C., and the precipitated salt was separated by filtration to obtain 2970 g of a compound.
The hydroxyl value of the obtained compound was 57.2 (calculated value: 56.1), and the degree of unsaturation was 1.98 (calculated value: 2.0). 2 compounds.
[0024]
Production Example 3
In a 5-liter autoclave, No. 2100 g (0.7 mol) of compound 2 and 59.4 g (1.1 mol) of sodium methylate were taken, and after the inside of the system was replaced with nitrogen gas, the temperature was raised to 100 ° C. while stirring, and 1 hour at 100 mmHg or less. Alcoholization was performed. Next, the inside of the system was brought to normal pressure with nitrogen gas, methyl chloride was blown from a cylinder, and the system was kept at 100 ° C. for 7 hours while adjusting the blowing tube so that the inside of the system became 1 kg / cm ² . Thereafter, the mixture was cooled to 60 ° C. while blowing nitrogen gas, and excess methyl chloride was distilled off. Thereafter, the pH was adjusted to 7.0 with a 10% hydrochloric acid aqueous solution, and dehydration was performed at 100 ° C. and 100 mmHg or less for 1 hour. Next, the mixture was cooled to 80 ° C., and the precipitated salt was separated by filtration to obtain 1900 g of a compound.
The hydroxyl value of the obtained compound was 1.3 (calculated value: 0), and the degree of unsaturation was 1.95 (calculated value: 1.97). Based on the results, No. Compound 3 was obtained.
[0025]
Production Examples 4 to 7
Hereinafter, by the same method as in Production Example 1, No. 1 shown in Table 1 was used. 4-No. Compound 7 was obtained. The analytical values are shown in Table 2.
[0026]
Example 1 (mercaptoacetic acid; HSCH ₂ COOH)
In a four-necked flask, 902 g (9.8 mol) of mercaptoacetic acid as a compound of the general formula (5) was added, and the temperature was maintained at 35 ° C. ± 5 ° C. while stirring. Then, Table 1 No. 995 g (0.25 mol) of the compound of the general formula (4) 1 was dissolved in 995 g of methanol, and the solution was added dropwise to a four-necked flask over 5 hours by a dropping funnel. After the completion of the dropwise addition, the reaction was further continued at 40 ± 5 ° C. for 5 hours.
Next, methanol was distilled off at 60 ± 10 ° C. under a reduced pressure of 200 mmHg or less, and then redissolved in 2000 g of chloroform. Next, the whole amount was transferred to a separating funnel, and washed three times with 1 liter of saturated saline to remove unreacted meercaptoacetic acid. Then, chloroform and water were distilled off at 110 ± 10 ° C. under a vacuum of 50 mmHg or less under a nitrogen atmosphere, and the precipitated salt was removed by filtration. 930 g of the compound shown in 1 were obtained.
The acid value of the obtained compound was 112.8 (calculated value 113.3), and the degree of unsaturation was 0.01 (calculated value 0). Tables 3, 4, and 5 show the reaction conditions, analysis values, and product structures. The measurement of the acid value was performed according to the method of JIS K-1557, 6.6 (1970). The reaction conditions, analysis values, and products are shown in Tables 3, 4, and 5, respectively.
[0027]
[Table 3]

[0028]
[Table 4]

[0029]
[Table 5]

[0030]
FIG. 4 shows a gel permeation chromatogram, FIG. 5 shows an infrared absorption spectrum, and FIG. 6 shows an NMR spectrum.
The measurement results of the infrared absorption spectrum are as follows.
The absorption of C = C at 1650 cm ^-1 has disappeared.
The measurement results of the ¹ H-NMR spectrum are as follows.
¹ H-NMR (δ (ppm), CDCl ₃ / TMS)
_{δ = 1.85ppm (-O-CH 2} C H 2 CH 2 -S-CH 2 -COOH)
_{δ = 2.75ppm (-O-CH 2} CH 2 C H 2 -S-CH 2 -COOH)
δ = 3.2 ppm (-O-CH 2 CH 2 CH 2 -S-C H 2 -COOH)
A comparison between FIGS. 1 to 3 and FIGS. 4 to 6 shows that the compound of Production Example 1 reacts with mercaptoacetic acid.
[0031]
Example 2 (3-mercaptopropionic acid; HSC ₂ H ₄ COOH)
530 g (5 mol) of 3-mercaptopropionic acid as a compound of the general formula (5) was placed in a four-necked flask, and the temperature was maintained at 35 ° C ± 5 ° C with stirring. Then, Table 1 No. 900 g (0.3 mol) of the compound of the formula (4) 2 was dissolved in 500 g of methanol, and the solution was added dropwise to a four-necked flask over 5 hours using a dropping funnel. After completion of the dropwise addition, the reaction was further continued at 40 ± 5 ° C. for 5 hours to continue the reaction.
Next, methanol was distilled off at 60 ± 10 ° C. under a reduced pressure of 200 mmHg or less, and then redissolved in 2000 g of chloroform. Next, the whole amount was transferred to a separating funnel and washed three times with 1 liter of saturated saline to remove unreacted 3-mercaptopropionic acid. Then, chloroform and water were distilled off at 110 ± 10 ° C. under a vacuum of 50 mmHg or less under a nitrogen atmosphere, and the precipitated salt was removed by filtration. 860 g of the compound shown in 2 were obtained.
The acid value of the obtained compound was 92.3 (calculated value 91.8), and the degree of unsaturation was 0.0 (calculated value 0).
[0032]
Example 3 (mercaptosuccinic acid = HSC (-H) (- COOH ) (- CH 2 COOH))
In a four-necked flask, 900 g (6 mol) of mercaptosuccinic acid as the compound of the formula (5) and 924 g of water were stirred and the temperature was maintained at 35 ° C ± 5 ° C. Then, Table 1 No. 995 g (0.25 mol) of the compound of the formula (4) 1 was dissolved in 450 g of water, and the solution was added dropwise to a four-necked flask by a dropping funnel over 5 hours. After completion of the dropwise addition, the reaction was further continued at 40 ± 5 ° C. for 5 hours to continue the reaction.
Next, 2000 g of chloroform was added, and the whole amount was transferred to a separating funnel and washed three times with 2 liters of saturated saline to remove unreacted mercaptosuccinic acid. Then, chloroform and water were distilled off at 110 ± 10 ° C. under a vacuum of 50 mmHg or less under a nitrogen atmosphere, and the precipitated salt was removed by filtration. 1110 g of the compound shown in No. 3 were obtained.
The acid value of the obtained compound was 198.4 (calculated value 202.8), and the degree of unsaturation was 0.02 (calculated value 0). Similarly, the results are shown in the table.
[0033]
Examples 4 to 8
In the same manner, using the raw materials in Table 1 and analyzing the compounds shown in Table 4 under the reaction conditions shown in Table 3, 4-No. Compound 7 was obtained. Examples 1 to 8 show that a polyoxyalkylene compound having a plurality of carboxyl groups was obtained.
[0034]
[Brief description of the drawings]
FIG. 1 is a gel permeation chromatogram of the compound of Production Example 1.
FIG. 2 is an infrared absorption spectrum of the compound of Production Example 1.
FIG. 3 is a ¹ H-NMR (nuclear magnetic resonance) spectrum diagram of the compound of Production Example 1.
FIG. 4 is a gel permeation chromatogram of the compound of Example 1.
FIG. 5 is an infrared absorption spectrum of the compound of Example 1.
FIG. 6 is a ¹ H-NMR spectrum of the compound of Example 1.

Claims (3)

A carboxyl group-containing polyoxyalkylene compound represented by the formula (1).

Wherein Z is a residue of a compound having 2 to 8 hydroxyl groups, A ¹ O and A ² O are one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms, and B ¹ O, B ² O is one or a mixture of two or more groups represented by the formula (2);

(However, R ¹ is an unsaturated hydrocarbon group having 2 to 5 carbon atoms)
C ¹ O and C ² O are one kind or a mixture of two or more kinds of groups represented by the formula (3);

(However, R ² may be the same or different from a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, alkylammonium or a hydrocarbon group having 1 to 24 carbon atoms, and R ³ may be an alkylene having 2 to 5 carbon atoms. And the group R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms or —CH (CH ₂ COOH) —.
R wherein C ¹ O is randomly added to part or all of A ¹ O or B ¹ O, and C ² O is randomly added to part or all of A ² O or B ² O ; Is a hydrocarbon group or an acyl group having 1 to 24 carbon atoms, m is an integer of 0 to 8, n is an integer of 0 to 8, m + n = 2 to 8, 0 ≦ a, 0 ≦ b, 0 ≦ i, 0 ≦ j, 0 ≦ p, 0 ≦ q, and am + bn = 1 to 1500, im + jn = 0 to 100, and pm + qn = 2 to 100 are satisfied. ] The carboxyl group-containing polyoxyalkylene compound according to claim 1, wherein R ⁴ is a methylene group or an ethylene group. A compound with 2 to 8 hydroxyl groups ^One O and A ^Two O and B ^One O and B ^Two A method for producing a carboxyl group-containing polyoxyalkylene compound represented by the formula (1), wherein a part or all of O is added at random and further reacted with a compound of the formula (5).

[Where Z is a residue of a compound having 2 to 8 hydroxyl groups, A ^One O, A ^Two O is one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms; ^One O, B ^Two O is represented by the formula (2) A mixture of one or more of the groups

(However, R ^One Is an unsaturated hydrocarbon group having 2 to 5 carbon atoms)
C ^One O, C ^Two O is one or a mixture of two or more groups represented by the formula (3):

(However, R ^Two Is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkylammonium or a hydrocarbon group having 1 to 24 carbon atoms, which may be the same or different; ^Three Is an alkylene group having 2 to 5 carbon atoms, R ^Four Is a divalent hydrocarbon group having 1 to 10 carbon atoms or -CH (CH _Two COOH)-. )
C ^One O is A ^One O or B ^One Random addition with some or all of O, and C ^Two O is A ^Two O or B ^Two R is a hydrocarbon group or an acyl group having 1 to 24 carbon atoms, m is an integer of 0 to 8, n is an integer of 0 to 8, and m + n = 2. 8, 0 ≦ a, 0 ≦ b, 0 ≦ i, 0 ≦ j, 0 ≦ p, 0 ≦ q, and am + bn = 1 to 1500, im + jn = 0 to 100, and pm + qn = 2 to 100 are satisfied. ]

(However, R ^Two May be the same or different and may be hydrogen, an alkali metal, an alkaline earth metal, ammonium, an organic ammonium or a hydrocarbon group having 1 to 24 carbon atoms; ^Four Is a divalent hydrocarbon group having 1 to 10 carbon atoms or -CH (CH _Two COOH)-. )

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