JP4287546B2 - Manufacturing method of glyceryl ether - Google Patents

Manufacturing method of glyceryl ether Download PDF

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Publication number
JP4287546B2
JP4287546B2 JP21202199A JP21202199A JP4287546B2 JP 4287546 B2 JP4287546 B2 JP 4287546B2 JP 21202199 A JP21202199 A JP 21202199A JP 21202199 A JP21202199 A JP 21202199A JP 4287546 B2 JP4287546 B2 JP 4287546B2
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palladium
glyceryl ether
phosphite
tertiary phosphine
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JP2001039914A (en
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宗尚 奥津
敦志 永澤
智人 木附
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Kao Corp
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Kao Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

【０００１】
【発明の属する技術分野】
本発明はグリセリルエーテルの製法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
モノアルキルグリセリルエーテルは乳化剤、分散剤、洗浄剤等として優れた非イオン性界面活性剤であり、その中でもモノオクチルグリセリルエーテルは特に有用なものの一つである。
【０００３】
モノアルキルグリセリルエーテルの製法としては、(1) アルコールとエピクロロヒドリン等のエピハロヒドリンからグリシジルエーテルを合成し、更に加水分解する方法が一般的である。またその他、(2) グリセリンとアルキルハライドを塩基を用いて反応させる方法、(3) アルコールとグリセリンを酸触媒により直接反応させる方法、(4) アルコールとグリシドールを酸又は塩基性触媒を用いて反応させる方法なども知られている。
【０００４】
しかし、(1) の方法では、グリシジルエーテルを選択的に合成することが難しく、また原料由来の有機塩素化物が混入するおそれもある。また、(2) の方法は、モノアルキルエーテルの選択的合成が困難であるだけでなく、大量に生成する塩の処理が必要であり、更に生成物が著しく着色するといった問題があり、(3) の方法は、同様にモノアルキルエーテルの選択的合成が困難で、ジアルキル体やα-分岐エーテル結合物のほか、アルコール同士が反応したジアルキルエーテルの副生が避けられないという問題があり、(4) の方法は、グリシドール自身の重合や生成物へのグリシドールの過剰付加を避けることが難しいといった問題がある。
【０００５】
一方、共役アルカジエンがアルコールやポリオールによってテロメル化し、1,7-又は2,7-アルカジエニルエーテルが得られることは知られているが、そのうち特表平6-509339号公報には、共役ジエンとポリオール、特にグリセリンを用いてテロメリゼーションによりオクタジエニルグリセリルエーテルを合成する方法が開示されている。そしてこのオクタジエニルグリセリルエーテルは水素添加によりオクチルグリセリルエーテルとすることが可能であるが、このグリセリンのテロメリゼーション法では、生成物がモノオクタジエニルグリセリルエーテルとジオクタジエニルグリセリルエーテル、更にはトリオクタジエニルグリセリルエーテルとの混合物になってしまい、選択的にモノオクタジエニルグリセリルエーテルのみを合成することが困難であった。また更にグリセリンを反応させるためにはイソプロピルアルコールのような第二級アルコールを溶媒として用いる必要があるため、より選択的に、簡便かつ安価にモノアルキルグリセリルエーテルを製造する方法が望まれていた。
【０００６】
【課題を解決するための手段】
本発明は、一般式(1)
【０００７】
【化２】

Figure 0004287546
【０００８】
〔式中、Ｒ1 及びＲ2 は同一又は異なって、水素原子又は炭素数１〜１０の炭化水素基を示す。ただし、Ｒ1 とＲ2 は同時に水素原子となることはなく、またこれらが連結して隣接する炭素原子とともに環を形成してもよい。〕
で表されるグリセリン誘導体に、パラジウム化合物及び第三級ホスフィン若しくはホスファイトの存在下、又はパラジウム−第三級ホスフィン錯体若しくはパラジウム−ホスファイト錯体の存在下、共役ジエンを反応させて、共役ジエンが２量化したアルカジエニル基を有するエーテル体を得る工程（以下、第一の工程という）の後、得られたエーテル体に対して、水素雰囲気中で第VIII族（８〜10族）元素を含有する触媒の存在下にアルカジエニル基を水素添加する工程、及び酸触媒の存在下にアセタール（又はケタール）を加水分解する工程を行うモノアルキルグリセリルエーテルの製法を提供するものである。
【０００９】
【発明の実施の形態】
第一の工程においては、グリセリン誘導体(1) と共役ジエンとを、パラジウム化合物及び第三級ホスフィン若しくはホスファイトの存在下、又はパラジウム−第三級ホスフィン錯体若しくはパラジウム−ホスファイト錯体の存在下に反応させることにより、グリセリン誘導体(1) のアルカジエニルエーテル化物が得られる。
【００１０】
本工程で使用されるグリセリン誘導体(1) は、例えばグリセリンと下記一般式(2)
【００１１】
【化３】
Figure 0004287546
【００１２】
〔式中、Ｒ1 及びＲ2 は前記と同じ意味を示す。〕
で表されるカルボニル化合物をp-トルエンスルホン酸等の酸触媒を用いて反応させることにより、容易に合成することができる。ただし、Ｒ1 が水素の場合は、混合物として2-アルキル-1,3-ジオキサン-5-オールが含有されやすくなるため、カルボニル化合物(2) としては、ケトンがより好ましい。
【００１３】
カルボニル化合物(2) としては、例えば、アセトン、メチルエチルケトン、メチルプロピルケトン、メチルイソプロピルケトン、メチルブチルケトン、メチルイソブチルケトン、ジエチルケトン、エチルプロピルケトン、エチルブチルケトン、ジプロピルケトン、ジイソプロピルケトン、ジブチルケトン、ジイソブチルケトン、ジペンチルケトン、ジヘキシルケトン等の非環状ケトンのほか、シクロペンタノン、シクロヘキサノン、メチルシクロヘキサノン、エチルシクロヘキサノン、プロピルシクロヘキサノン、ブチルシクロヘキサノン等のアルキル基が置換してもよい５又は６員の環状ケトンが挙げられるが、アセトン、メチルエチルケトン、メチルイソブチルケトン等のＲ1 及びＲ2 が炭素数１〜６、特に炭素数１〜４のアルキル基であるジアルキルケトンがより好ましい。
【００１４】
共役ジエンとしては、1,3-アルカジエン、2,4-アルカジエン等が挙げられるが、炭素数４〜６の1,3-アルカジエンが好ましく、具体的には1,3-ブタジエン、1,3-ペンタジエン、1,3-ヘキサジエン、イソプレン等が挙げられる。このうち1,3-ブタジエンが特に好ましく用いられ、この場合に非イオン界面活性剤として優れた性能を有するモノオクチルグリセリルエーテルを製造することができる。
【００１５】
第一の工程で使用されるパラジウム化合物としては、例えばビス(アセチルアセトナト)パラジウム(II)、酢酸パラジウム(II)、塩化パラジウム(II)等が挙げられるが、なかでもビス(アセチルアセトナト)パラジウム(II)及び酢酸パラジウムが好ましく、特に塩基触媒共存の条件においてはビス(アセチルアセトナト)パラジウム(II)が好ましい。またパラジウム錯体としては、例えばテトラキス(トリフェニルホスフィン)パラジウム(0)等が挙げられる。これらパラジウム化合物又はパラジウム錯体の使用量は、グリセリン誘導体に対しモル比率で0.0001〜0.01、特に0.001〜0.01が好ましい。
【００１６】
また第三級ホスフィン又はホスファイトとしては、トリメチルホスフィン、トリエチルホスフィン、トリプロピルホスフィン、トリブチルホスフィン等の脂肪族トリアルキルホスフィン；ジメチルフェニルホスフィン、メチルジフェニルホスフィン、ジエチルフェニルホスフィン、エチルジフェニルホスフィン、トリフェニルホスフィン等の芳香族ホスフィン；1,2-ビス(ジフェニルホスフィノ)エタン、1,3-ビス(ジフェニルホスフィノ)プロパン、1,4-ビス(ジフェニルホスフィノ)ブタン、1,4-ビス(ジメチルホスフィノ)ブタン、1,2-ビス(ジメチルホスフィノ)エタン等の二座配位子となるホスフィン；これらと同様の構造を持つトリアルキルホスファイト等が挙げられる。またスルホン酸基やカルボキシル基を置換基として持つトリアリールホスフィンも回収等の点から好ましい。第三級ホスフィン又はホスファイトのパラジウム化合物に対する使用量としては、パラジウム化合物に対して0.1〜４モル当量、特に１〜2.5モル当量が好ましい。また二座配位子となるホスフィン又はホスファイトの場合は、パラジウム化合物に対して0.1〜２モル当量、特に0.5〜1.5モル当量が好ましい。
【００１７】
第一の工程における反応系には、塩基を共存させるのが好ましく、このような塩基としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；ナトリウムメトキシド、カリウム t-ブトキシド等の低級アルコール又は第３級アルコールから導かれるアルカリ金属アルコキシド；その他水素化ナトリウム、金属ナトリウム等が挙げられるが、なかでもアルカリ金属アルコキシドが好ましい。これら塩基の使用量としては、グリセリン誘導体(1) に対して0.1〜10重量％が好ましい。
【００１８】
共役ジエンは、オートクレーブ等の反応容器中に一括して仕込んでも、また連続的に導入してもよいが、グリセリン誘導体(1)に対して1.0〜3.0モル当量（グリセリン誘導体(1) １モルに対して２〜６モル）となるように仕込むのが好ましい。
【００１９】
グリセリン誘導体(1)と共役ジエンを反応させる際の反応温度は、10〜100℃、特に40〜90℃に保つのが好ましい。また未反応の共役ジエンは、反応後に低沸点物として回収することも可能である。
【００２０】
続く第二及び第三の工程においては、以上の第一の工程で生成したアルカジエニルエーテル化物に対し、(a)水素雰囲気下で第VIII族（８〜10族）元素を含有する触媒によるアルカジエニル基の水素添加、及び(b)酸触媒の存在下にアセタール（又はケタール）の加水分解を行うことにより、目的のモノアルキルグリセリルエーテルを得る。これら(a)と(b)の順序は限定されず、すなわちいずれを第二の工程とし、第三の工程としてもよいが、(a)アルカジエニル基の水素添加の後に、(b)アセタール（又はケタール）の加水分解を行うのがより好ましい。
【００２１】
(a)のアルカジエニル基の水素添加工程で使用する第VIII族（８〜10族）元素を含有する触媒としては、Pd、Rh、Ru、Ni、Pt等の金属が低酸化数状態で含有されているものが挙げられ、特にこれらの金属がカーボン、ゼオライト、シリカアルミナ等に１〜10重量％担持されたものや、ラネーニッケル、それらの金属の酸化物が好ましい。触媒の使用量はアルカジエニルエーテル化物に対して0.1〜10重量％が好ましい。また水素圧は特に制限されないが、常圧〜20MPaの範囲が好ましい。
【００２２】
(b)のアセタール（又はケタール）の加水分解工程で使用する酸触媒としては、p-トルエンスルホン酸、硫酸等の通常用いられるものが挙げられ、また加水分解の方法も常法に従うことが好ましいが、工業的な観点から、水蒸気を用いて加水分解とケトンの回収を同時に行う方法も好ましい。
【００２３】
【実施例】
実施例１
１Ｌオートクレーブ中に2,2-ジメチル-4-ヒドロキシメチル-1,3-ジオキソラン250ｇ（1.9mol）、ビス(アセチルアセトナト)パラジウム(II)152mg（0.5mmol）、トリブチルホスフィン202mg（1.0mmol）及びt-ブトキシカリウム5.0ｇ（0.05mol）を加え、更に1,3-ブタジエン300ｇ（5.6mol）を一括で導入し、攪拌しながら70℃に昇温した。オートクレーブ内の圧力は初期に0.7MPaを示したが徐々に減少した。70℃で10時間攪拌後、室温まで放冷し、未反応のブタジエン及び副生したオクタトリエンを減圧下で除き、更に水洗して、425ｇの2,2-ジメチル-4-ヒドロキシメチル-1,3-ジオキソランのオクタジエニルエーテル化物を淡赤黄色の透明オイルとして得た。
得られたオクタジエニルエーテル化物300ｇ及び５％Pd-シリカアルミナ（NEケムキャット社製）10ｇを500mlオートクレーブに加え、１〜５MPaの圧力の水素雰囲気下、25〜70℃で12時間攪拌した。反応終了後、触媒をろ過により除去し、300ｇの2,2-ジメチル-4-ヒドロキシメチル-1,3-ジオキソランのオクチルエーテル化物を無色透明オイルとして得た。
オクチルエーテル化物300ｇ（1.2mol）、水1000ｇ及びp-トルエンスルホン酸3.0ｇを１Ｌ四つ口フラスコに入れ、50℃、200mmHgの減圧下、12時間加水分解を行った。反応終了後、更に等量の温水で水洗し、250ｇのモノオクチルグリセリルエーテルを無色透明オイルとして得た。GC分析より純度は97％であり、モノ(2-オクチル)グリセリルエーテルを３％含有していた。
【００２４】
比較例１
１Ｌオートクレーブ中にグリセリン150ｇ（1.6mol）、2-プロパノール230ｇ、ビス(アセチルアセトナト)パラジウム(II) 60mg（0.2mmol）及びトリフェニルホスフィン103mg（0.4mmol）を加え、更に1,3-ブタジエン100ｇ（1.85mol）を一括で導入し、攪拌しながら70℃に昇温した。オートクレーブ内の圧力は初期に0.7MPaを示したが徐々に減少し、３時間後に圧力は常圧となった。室温まで放冷後、生成物に10ｇの５％Pd-Cを加えて、２MPaの圧力の水素雰囲気下、70℃で10時間水素添加を行った。反応終了後GC分析した結果、反応混合物中のモノオクチルグリセリルエーテルは55％であり、ジオクチルグリセリルエーテルが22％副生しており、未反応のグリセリンが14％残存していた。
【００２５】
実施例２
実施例１において、第一の工程をトリブチルホスフィンに代えてトリフェニルホスフィン262mg（1.0mmol）を用いて同様に行い、415ｇのオクタジエニルエーテル化物を淡赤黄色の透明オイルとして得た。
続く水素添加工程を70℃で15時間行う以外は実施例１と同様に行い、300ｇのオクチルエーテル化物を無色透明オイルとして得、加水分解工程は実施例１と全く同様に行って、250ｇのモノオクチルグリセリルエーテルを無色透明オイルとして得た。GC分析より純度は97％であり、モノ(2-オクチル)グリセリルエーテルを３％含有していた。
【００２６】
実施例３
１Ｌオートクレーブ中に、2-メチル-2-エチル-4-ヒドロキシメチル-1,3-ジオキソラン275ｇ（1.9mol）及びナトリウムメチラートの28％メタノール溶液5.0ｇ（0.05mol）を加え、200mmHgの減圧下、90℃でメタノールを留去した。更にビス(アセチルアセトナト)パラジウム(II)152mg（0.5mmol）及びトリブチルホスフィン202mg（1.0mmol）を加え、更に1,3-ブタジエン300ｇ（5.6mol）を一括で導入し、攪拌しながら、70℃に昇温した。オートクレーブ内の圧力は初期に0.7MPaを示したが徐々に減少した。70℃で10時間攪拌後、室温まで放冷し、未反応のブタジエン及び副生したオクタトリエンを減圧下で除き、更に水洗して、450ｇの2-メチル-2-エチル-4-ヒドロキシメチル-1,3-ジオキソランのオクタジエニルエーテル化物を得た。
続く水素添加工程を実施例１と全く同様に行い、300ｇの2-メチル-2-エチル-4-ヒドロキシメチル-1,3-ジオキソランのオクチルエーテル化物を得、加水分解工程をp-トルエンスルホン酸に代えて硫酸１ｇを用いて実施例１と同様に行い、235ｇのモノオクチルグリセリルエーテルを無色透明オイルとして得た。GC分析より純度は97％であり、モノ(2-オクチル)グリセリルエーテルを３％含有していた。
【００２７】
実施例４
実施例３において、第一の工程をトリブチルホスフィンに代えてジメチルフェニルホスフィン138mg（1.0mmol）を用いて同様に行い、450ｇのオクタジエニルエーテル化物を得た。
続く水素添加工程を実施例３と全く同様に行い、300ｇのオクチルエーテル化物を得、加水分解工程も実施例３と全く同様に行って、235ｇのモノオクチルグリセリルエーテルを無色透明オイルとして得た。GC分析より純度は94％であり、モノ(2-オクチル)グリセリルエーテルを６％含有していた。
【００２８】
実施例５
実施例１において、第一の工程をトリブチルホスフィンに代えて1,2-ビス(ジフェニルホスフィノ)ブタン400mg（1.0mmol）を用いる以外は同様に行い、420ｇのオクタジエニルエーテル化物を得た。
続く水素添加工程を実施例１と全く同様に行い、300ｇのオクチルエーテル化物を得、加水分解工程も実施例１と全く同様に行って、250ｇのモノオクチルグリセリルエーテルを無色透明オイルとして得た。GC分析より純度は97％であり、モノ(2-オクチル)グリセリルエーテルを３％含有していた。
【００２９】
実施例６
実施例１において、第一の工程をビス(アセチルアセトナト)パラジウム(II)とトリブチルホスフィンの組合わせに代えてテトラキス(トリフェニルホスフィン)パラジウム(0) 450mg（0.39mmol）を用いて同様に行い、420ｇのオクタジエニルエーテル化物を得た。
続く水素添加工程を実施例１と全く同様に行い、300ｇのオクチルエーテル化物を得、加水分解工程も実施例１と全く同様に行って、250ｇのモノオクチルグリセリルエーテルを無色透明オイルとして得た。GC分析より純度は97％であり、モノ(2-オクチル)グリセリルエーテルを３％含有していた。
【００３０】
実施例７
実施例１において、第一の工程をビス(アセチルアセトナト)パラジウム(II)に代えて酢酸パラジウム(II) 112mg（0.5mmol）を用い、トリブチルホスフィンに代えてトリフェニルホスフィン262mg（1.0mmol）を用い、塩基を用いない以外は同様に行い、405ｇのオクタジエニルエーテル化物を得た。
得られたオクタジエニルエーテル化物300ｇ及び酸化パラジウム(II) ２ｇを500mlオートクレーブに加え、常圧水素雰囲気下、室温で24時間攪拌した。反応終了後、触媒をろ過により除去し、300ｇのオクチルエーテル化物を無色透明オイルとして得た。
加水分解工程は実施例１と全く同様に行い、250ｇのモノオクチルグリセリルエーテルを無色透明オイルとして得た。GC分析より純度は95％であり、モノ(2-オクチル)グリセリルエーテルを５％含有していた。
【００３１】
実施例８
１Ｌオートクレーブ中に2-メチル-2-エチル-4-ヒドロキシメチル-1,3-ジオキソラン275ｇ（1.9mol）、ビス(アセチルアセトナト)パラジウム(II)152mg（0.5mmol）、トリブチルホスフィン202mg（1.0mmol）及びt-ブトキシカリウム5.0ｇ（0.05mol）を加え、更にイソプレン380ｇ（5.6mol）を一括で導入し、窒素で置換した後、70℃に昇温した。そのまま70℃で16時間攪拌後、室温まで放冷し、未反応のイソプレン及び副生したジメチルオクタトリエンを減圧下で除き、更に水洗して、470ｇの2-メチル-2-エチル-4-ヒドロキシメチル-1,3-ジオキソランの(ジメチルオクタジエニル)エーテル化物を赤黄色の透明オイルとして得た。
得られた(ジメチルオクタジエニル)エーテル化物300ｇ及び５％Pd-シリカアルミナ（NEケムキャット社製）10ｇを500mlオートクレーブに加え、１〜５MPaの圧力の水素雰囲気下、25〜70℃で12時間攪拌した。反応終了後、触媒をろ過により除去し、300ｇの２-メチル-2-エチル-4-ヒドロキシメチル-1,3-ジオキソランの(ジメチルオクチル)エーテル化物を淡黄色透明オイルとして得た。
得られた(ジメチルオクチル)エーテル化物300ｇ（1.2mol）、水1000ｇ及び硫酸１ｇを２Ｌ四つ口フラスコに入れ、50℃、200mmHgの減圧下、12時間加水分解を行った。反応終了後、更に等量の温水で水洗し、255ｇのモノ(ジメチルオクチル)グリセリルエーテルを淡黄色透明オイルとして得た。この生成モノ(ジメチルオクチル)グリセリルエーテルは、(3,7-ジメチル-1-オクチル)グリセリルエーテル、(3,6-ジメチル-1-オクチル)グリセリルエーテル等のメチル基の位置が異なる異性体の混合物として得られ、(ジメチルオクチル)グリセリルエーテルとしての純度はGC分析より96％であった。
【００３２】
【発明の効果】
本発明によれば、より選択的に、簡便かつ安価に、しかも溶媒を用いることなくモノアルキルグリセリルエーテルを製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing glyceryl ether.
[0002]
[Prior art and problems to be solved by the invention]
Monoalkyl glyceryl ether is a nonionic surfactant excellent as an emulsifier, a dispersant, a cleaning agent, etc. Among them, monooctyl glyceryl ether is one of particularly useful ones.
[0003]
As a method for producing a monoalkyl glyceryl ether, (1) a method in which glycidyl ether is synthesized from an alcohol and an epihalohydrin such as epichlorohydrin and then hydrolyzed is generally used. In addition, (2) a method of reacting glycerin and alkyl halide using a base, (3) a method of reacting alcohol and glycerin directly with an acid catalyst, and (4) a reaction of alcohol and glycidol using an acid or basic catalyst. The method of making it known is also known.
[0004]
However, in the method (1), it is difficult to selectively synthesize glycidyl ether, and organic chlorinated products derived from raw materials may be mixed. In addition, the method (2) not only makes it difficult to selectively synthesize monoalkyl ethers, but also requires the treatment of a large amount of salt, and further has a problem that the product is markedly colored. ) Method is similarly difficult to selectively synthesize monoalkyl ethers, and there is a problem that dialkyl ethers and α-branched ether conjugates as well as by-products of dialkyl ethers reacted with alcohols cannot be avoided. The method 4) has a problem that it is difficult to avoid polymerization of glycidol itself and excessive addition of glycidol to the product.
[0005]
On the other hand, it is known that conjugated alkadienes are telomerized with alcohols or polyols to give 1,7- or 2,7-alkadienyl ethers. And a method of synthesizing octadienyl glyceryl ether by telomerization using polyol and in particular glycerin. And this octadienyl glyceryl ether can be converted to octyl glyceryl ether by hydrogenation, but in this glycerin telomerization method, the product is monooctadienyl glyceryl ether and dioctadienyl glyceryl ether, Became a mixture with trioctadienyl glyceryl ether, and it was difficult to selectively synthesize only monooctadienyl glyceryl ether. Further, in order to further react glycerin, it is necessary to use a secondary alcohol such as isopropyl alcohol as a solvent. Therefore, a more selective and simple method for producing monoalkyl glyceryl ether has been desired.
[0006]
[Means for Solving the Problems]
The present invention relates to general formula (1)
[0007]
[Chemical formula 2]
Figure 0004287546
[0008]
[Wherein, R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, R 1 and R 2 do not simultaneously become hydrogen atoms, and they may be linked to form a ring together with adjacent carbon atoms. ]
Is reacted with a conjugated diene in the presence of a palladium compound and a tertiary phosphine or phosphite, or in the presence of a palladium-tertiary phosphine complex or a palladium-phosphite complex. After the step of obtaining an ether body having a dimerized alkadienyl group (hereinafter referred to as the first step), the obtained ether body contains a Group VIII (Group 8 to 10) element in a hydrogen atmosphere. The present invention provides a method for producing a monoalkyl glyceryl ether which comprises a step of hydrogenating an alkadienyl group in the presence of a catalyst and a step of hydrolyzing an acetal (or ketal) in the presence of an acid catalyst.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the first step, the glycerol derivative (1) and the conjugated diene are combined in the presence of a palladium compound and a tertiary phosphine or phosphite, or in the presence of a palladium-tertiary phosphine complex or a palladium-phosphite complex. By reacting, an alkadienyl etherified product of the glycerin derivative (1) is obtained.
[0010]
The glycerin derivative (1) used in this step is, for example, glycerin and the following general formula (2)
[0011]
[Chemical 3]
Figure 0004287546
[0012]
[Wherein, R 1 and R 2 have the same meaning as described above. ]
Can be easily synthesized by reacting the carbonyl compound represented by the formula (1) with an acid catalyst such as p-toluenesulfonic acid. However, when R 1 is hydrogen, 2-alkyl-1,3-dioxane-5-ol is likely to be contained as a mixture, so that the carbonyl compound (2) is more preferably a ketone.
[0013]
Examples of the carbonyl compound (2) include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl propyl ketone, ethyl butyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone. In addition to acyclic ketones such as diisobutyl ketone, dipentyl ketone, and dihexyl ketone, 5- or 6-membered cyclics that may be substituted by an alkyl group such as cyclopentanone, cyclohexanone, methylcyclohexanone, ethylcyclohexanone, propylcyclohexanone, and butylcyclohexanone Although ketone, acetone, methyl ethyl ketone, R 1 and R 2 is 1 to 6 carbon atoms such as methyl isobutyl ketone, in particular der alkyl group having 1 to 4 carbon atoms Dialkyl ketones is more preferable.
[0014]
Examples of the conjugated diene include 1,3-alkadiene, 2,4-alkadiene, etc., and 1,3-alkadiene having 4 to 6 carbon atoms is preferable, specifically 1,3-butadiene, 1,3- Examples include pentadiene, 1,3-hexadiene, and isoprene. Of these, 1,3-butadiene is particularly preferably used. In this case, monooctyl glyceryl ether having excellent performance as a nonionic surfactant can be produced.
[0015]
Examples of the palladium compound used in the first step include bis (acetylacetonato) palladium (II), palladium (II) acetate, palladium (II) chloride, etc., among which bis (acetylacetonato) Palladium (II) and palladium acetate are preferred, and bis (acetylacetonato) palladium (II) is particularly preferred under the conditions of coexistence with a base catalyst. Examples of the palladium complex include tetrakis (triphenylphosphine) palladium (0). The amount of these palladium compounds or palladium complexes used is preferably from 0.0001 to 0.01, particularly preferably from 0.001 to 0.01, in terms of a molar ratio to the glycerol derivative.
[0016]
Tertiary phosphine or phosphite includes aliphatic trialkylphosphine such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine; dimethylphenylphosphine, methyldiphenylphosphine, diethylphenylphosphine, ethyldiphenylphosphine, triphenylphosphine. Aromatic phosphines such as 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,4-bis (dimethylphosphine) Phosphine) butane, 1,2-bis (dimethylphosphino) ethane and other bidentate phosphines; trialkyl phosphites having the same structure as these. Triarylphosphine having a sulfonic acid group or a carboxyl group as a substituent is also preferable from the viewpoint of recovery. As the usage-amount with respect to the palladium compound of tertiary phosphine or a phosphite, 0.1-4 molar equivalent with respect to a palladium compound, Especially 1-2.5 molar equivalent is preferable. Moreover, in the case of the phosphine or phosphite used as a bidentate ligand, 0.1-2 molar equivalent with respect to a palladium compound, Especially 0.5-1.5 molar equivalent is preferable.
[0017]
The reaction system in the first step preferably contains a base. Examples of such a base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium methoxide, potassium t-butoxide and the like. Alkali metal alkoxides derived from lower alcohols or tertiary alcohols; other examples include sodium hydride and sodium metal, among which alkali metal alkoxides are preferred. The amount of these bases used is preferably 0.1 to 10% by weight based on the glycerin derivative (1).
[0018]
The conjugated diene may be charged all at once in a reaction vessel such as an autoclave or may be continuously introduced. The conjugated diene is 1.0 to 3.0 molar equivalents per 1 mole of the glycerin derivative (1). 2 to 6 mol) is preferably charged.
[0019]
The reaction temperature when the glycerin derivative (1) is reacted with the conjugated diene is preferably maintained at 10 to 100 ° C, particularly 40 to 90 ° C. Unreacted conjugated diene can also be recovered as a low boiling point product after the reaction.
[0020]
In the subsequent second and third steps, (a) a catalyst containing a Group VIII (Group 8-10) element in a hydrogen atmosphere with respect to the alkadienyl etherified product formed in the first step above. The target monoalkyl glyceryl ether is obtained by hydrogenation of the alkadienyl group and (b) hydrolysis of the acetal (or ketal) in the presence of an acid catalyst. The order of these (a) and (b) is not limited, that is, either may be the second step and may be the third step. (A) After hydrogenation of the alkadienyl group, (b) an acetal (or More preferably, the ketal) is hydrolyzed.
[0021]
As a catalyst containing a Group VIII (Group 8-10) element used in the hydrogenation step of the alkadienyl group in (a), metals such as Pd, Rh, Ru, Ni, Pt are contained in a low oxidation number state. In particular, those in which these metals are supported on carbon, zeolite, silica alumina or the like in an amount of 1 to 10% by weight, Raney nickel, and oxides of these metals are preferable. The amount of the catalyst used is preferably 0.1 to 10% by weight based on the alkadienyl etherified product. The hydrogen pressure is not particularly limited, but is preferably in the range of normal pressure to 20 MPa.
[0022]
Examples of the acid catalyst used in the acetal (or ketal) hydrolysis step (b) include commonly used ones such as p-toluenesulfonic acid and sulfuric acid, and the hydrolysis method is preferably in accordance with a conventional method. However, from the industrial viewpoint, a method of simultaneously performing hydrolysis and recovery of ketones using water vapor is also preferred.
[0023]
【Example】
Example 1
In a 1 L autoclave, 250 g (1.9 mol) of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, 152 mg (0.5 mmol) of bis (acetylacetonato) palladium (II), 202 mg (1.0 mmol) of tributylphosphine and t-Butoxy potassium (5.0 g, 0.05 mol) was added, and 1,3-butadiene (300 g, 5.6 mol) was added all at once, and the temperature was raised to 70 ° C. with stirring. The pressure in the autoclave initially showed 0.7 MPa, but gradually decreased. After stirring at 70 ° C. for 10 hours, the mixture was allowed to cool to room temperature, unreacted butadiene and by-produced octatriene were removed under reduced pressure, further washed with water, and 425 g of 2,2-dimethyl-4-hydroxymethyl-1, An octadienyl etherified product of 3-dioxolane was obtained as a pale red yellow transparent oil.
300 g of the obtained octadienyl ether compound and 10 g of 5% Pd-silica alumina (manufactured by NE Chemcat) were added to a 500 ml autoclave and stirred at 25 to 70 ° C. for 12 hours in a hydrogen atmosphere at a pressure of 1 to 5 MPa. After completion of the reaction, the catalyst was removed by filtration to obtain 300 g of octyl etherified product of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane as a colorless transparent oil.
300 g (1.2 mol) of octyl etherified product, 1000 g of water and 3.0 g of p-toluenesulfonic acid were placed in a 1 L four-necked flask and hydrolyzed under reduced pressure at 50 ° C. and 200 mmHg for 12 hours. After completion of the reaction, the mixture was further washed with an equal amount of warm water to obtain 250 g of monooctyl glyceryl ether as a colorless transparent oil. According to GC analysis, the purity was 97%, and it contained 3% mono (2-octyl) glyceryl ether.
[0024]
Comparative Example 1
In a 1 L autoclave, 150 g (1.6 mol) of glycerin, 230 g of 2-propanol, 60 mg (0.2 mmol) of bis (acetylacetonato) palladium (II) and 103 mg (0.4 mmol) of triphenylphosphine are added, and 100 g of 1,3-butadiene is further added. (1.85 mol) was introduced all at once, and the temperature was raised to 70 ° C. while stirring. The pressure in the autoclave initially showed 0.7 MPa, but gradually decreased, and after 3 hours, the pressure became normal. After allowing to cool to room temperature, 10 g of 5% Pd—C was added to the product, and hydrogenated at 70 ° C. for 10 hours in a hydrogen atmosphere at a pressure of 2 MPa. As a result of GC analysis after completion of the reaction, monooctyl glyceryl ether in the reaction mixture was 55%, dioctyl glyceryl ether was by-produced by 22%, and unreacted glycerin remained 14%.
[0025]
Example 2
In Example 1, the first step was carried out in the same manner using 262 mg (1.0 mmol) of triphenylphosphine instead of tributylphosphine, and 415 g of octadienyl etherified product was obtained as a pale red yellow transparent oil.
Except that the subsequent hydrogenation step was carried out at 70 ° C. for 15 hours, it was carried out in the same manner as in Example 1 to obtain 300 g of octyl etherified product as a colorless transparent oil, and the hydrolysis step was carried out in exactly the same manner as in Example 1 to obtain 250 g of monoester. Octyl glyceryl ether was obtained as a colorless transparent oil. According to GC analysis, the purity was 97%, and it contained 3% mono (2-octyl) glyceryl ether.
[0026]
Example 3
In a 1 L autoclave, add 275 g (1.9 mol) of 2-methyl-2-ethyl-4-hydroxymethyl-1,3-dioxolane and 5.0 g (0.05 mol) of a 28% methanol solution of sodium methylate, and under reduced pressure of 200 mmHg. The methanol was distilled off at 90 ° C. Further, 152 mg (0.5 mmol) of bis (acetylacetonato) palladium (II) and 202 mg (1.0 mmol) of tributylphosphine were added, and 300 g (5.6 mol) of 1,3-butadiene was introduced all at once, while stirring at 70 ° C. The temperature was raised to. The pressure in the autoclave initially showed 0.7 MPa, but gradually decreased. After stirring at 70 ° C. for 10 hours, the mixture was allowed to cool to room temperature, unreacted butadiene and by-produced octatriene were removed under reduced pressure, washed with water, and 450 g of 2-methyl-2-ethyl-4-hydroxymethyl- An octadienyl etherified product of 1,3-dioxolane was obtained.
The subsequent hydrogenation step was performed in exactly the same manner as in Example 1 to obtain 300 g of octyl etherified product of 2-methyl-2-ethyl-4-hydroxymethyl-1,3-dioxolane, and the hydrolysis step was carried out with p-toluenesulfonic acid. Instead of 1 g of sulfuric acid, the same procedure as in Example 1 was carried out to obtain 235 g of monooctylglyceryl ether as a colorless transparent oil. According to GC analysis, the purity was 97%, and it contained 3% mono (2-octyl) glyceryl ether.
[0027]
Example 4
In Example 3, the first step was carried out in the same manner using 138 mg (1.0 mmol) of dimethylphenylphosphine instead of tributylphosphine, and 450 g of octadienyl etherified product was obtained.
The subsequent hydrogenation step was performed in exactly the same manner as in Example 3 to obtain 300 g of octyl etherified product, and the hydrolysis step was also performed in exactly the same manner as in Example 3 to obtain 235 g of monooctyl glyceryl ether as a colorless transparent oil. According to GC analysis, the purity was 94% and it contained 6% mono (2-octyl) glyceryl ether.
[0028]
Example 5
In Example 1, the first step was carried out in the same manner except that 400 mg (1.0 mmol) of 1,2-bis (diphenylphosphino) butane was used in place of tributylphosphine, and 420 g of octadienyl etherified product was obtained.
The subsequent hydrogenation step was performed in exactly the same manner as in Example 1 to obtain 300 g of octyl etherified product, and the hydrolysis step was also performed in exactly the same manner as in Example 1 to obtain 250 g of monooctyl glyceryl ether as a colorless transparent oil. According to GC analysis, the purity was 97%, and it contained 3% mono (2-octyl) glyceryl ether.
[0029]
Example 6
In Example 1, the first step was similarly carried out using 450 mg (0.39 mmol) of tetrakis (triphenylphosphine) palladium (0) instead of the combination of bis (acetylacetonato) palladium (II) and tributylphosphine. 420 g of octadienyl etherified product was obtained.
The subsequent hydrogenation step was performed in exactly the same manner as in Example 1 to obtain 300 g of octyl etherified product, and the hydrolysis step was also performed in exactly the same manner as in Example 1 to obtain 250 g of monooctyl glyceryl ether as a colorless transparent oil. According to GC analysis, the purity was 97%, and it contained 3% mono (2-octyl) glyceryl ether.
[0030]
Example 7
In Example 1, 112 mg (0.5 mmol) of palladium (II) acetate was used instead of bis (acetylacetonato) palladium (II) in the first step, and 262 mg (1.0 mmol) of triphenylphosphine was used instead of tributylphosphine. Used in the same manner except that no base was used, to obtain 405 g of octadienyl etherified product.
300 g of the obtained octadienyl ether compound and 2 g of palladium (II) oxide were added to a 500 ml autoclave, and the mixture was stirred at room temperature for 24 hours under a normal pressure hydrogen atmosphere. After completion of the reaction, the catalyst was removed by filtration to obtain 300 g of octyl etherified product as a colorless transparent oil.
The hydrolysis step was performed in exactly the same manner as in Example 1 to obtain 250 g of monooctyl glyceryl ether as a colorless transparent oil. According to GC analysis, the purity was 95%, and it contained 5% mono (2-octyl) glyceryl ether.
[0031]
Example 8
In a 1 L autoclave, 2-methyl-2-ethyl-4-hydroxymethyl-1,3-dioxolane 275 g (1.9 mol), bis (acetylacetonato) palladium (II) 152 mg (0.5 mmol), tributylphosphine 202 mg (1.0 mmol) ) And 5.0 g (0.05 mol) of t-butoxypotassium were added, and 380 g (5.6 mol) of isoprene was introduced all at once, followed by replacement with nitrogen, and the temperature was raised to 70 ° C. After stirring at 70 ° C. for 16 hours, the mixture was allowed to cool to room temperature, unreacted isoprene and by-produced dimethyloctatriene were removed under reduced pressure, and further washed with water to give 470 g of 2-methyl-2-ethyl-4-hydroxy. A (dimethyloctadienyl) etherified product of methyl-1,3-dioxolane was obtained as a red-yellow transparent oil.
300 g of the obtained (dimethyloctadienyl) etherification product and 10 g of 5% Pd-silica alumina (manufactured by NE Chemcat) were added to a 500 ml autoclave and stirred at 25 to 70 ° C. for 12 hours in a hydrogen atmosphere at a pressure of 1 to 5 MPa. did. After completion of the reaction, the catalyst was removed by filtration to obtain 300 g of (dimethyloctyl) etherified product of 2-methyl-2-ethyl-4-hydroxymethyl-1,3-dioxolane as a pale yellow transparent oil.
300 g (1.2 mol) of the obtained (dimethyloctyl) etherified product, 1000 g of water and 1 g of sulfuric acid were placed in a 2 L four-necked flask and hydrolyzed under reduced pressure at 50 ° C. and 200 mmHg for 12 hours. After completion of the reaction, the mixture was further washed with an equal amount of warm water to obtain 255 g of mono (dimethyloctyl) glyceryl ether as a pale yellow transparent oil. The resulting mono (dimethyloctyl) glyceryl ether is a mixture of isomers having different methyl groups such as (3,7-dimethyl-1-octyl) glyceryl ether and (3,6-dimethyl-1-octyl) glyceryl ether. The purity as (dimethyloctyl) glyceryl ether was 96% by GC analysis.
[0032]
【The invention's effect】
According to the present invention, monoalkyl glyceryl ether can be produced more selectively, simply and inexpensively, and without using a solvent.

Claims (5)

一般式(1)
Figure 0004287546
〔式中、Ｒ1 及びＲ2 は同一又は異なって、水素原子又は炭素数１〜１０の炭化水素基を示す。ただし、Ｒ1 とＲ2 は同時に水素原子となることはなく、またこれらが連結して隣接する炭素原子とともに環を形成してもよい。〕
で表されるグリセリン誘導体に、パラジウム化合物及び第三級ホスフィン若しくはホスファイトの存在下、又はパラジウム−第三級ホスフィン錯体若しくはパラジウム−ホスファイト錯体の存在下、共役ジエンを反応させて、共役ジエンが２量化したアルカジエニル基を有するエーテル体を得る工程（第一の工程という）の後、得られたエーテル体に対して、水素雰囲気中で第VIII族（８〜10族）元素を含有する触媒の存在下にアルカジエニル基を水素添加する工程、及び酸触媒の存在下にアセタール（又はケタール）を加水分解する工程を行うモノアルキルグリセリルエーテルの製法。General formula (1)
Figure 0004287546
 [Wherein, R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, R 1 and R 2 do not simultaneously become hydrogen atoms, and they may be linked to form a ring together with adjacent carbon atoms. ]
Is reacted with a conjugated diene in the presence of a palladium compound and a tertiary phosphine or phosphite, or in the presence of a palladium-tertiary phosphine complex or a palladium-phosphite complex. After the step of obtaining an ether body having a dimerized alkadienyl group (referred to as the first step), the obtained ether body is subjected to a catalyst containing a Group VIII (Group 8 to 10) element in a hydrogen atmosphere. A process for producing a monoalkyl glyceryl ether, comprising a step of hydrogenating an alkadienyl group in the presence and a step of hydrolyzing an acetal (or ketal) in the presence of an acid catalyst. 第一の工程において、反応系に塩基を共存させる請求項１記載のモノアルキルグリセリルエーテルの製法。The process for producing a monoalkyl glyceryl ether according to claim 1, wherein a base is allowed to coexist in the reaction system in the first step. 第一の工程において、反応系にパラジウム化合物及び第三級ホスフィン若しくはホスファイトを共存させる場合、第三級ホスフィン又はホスファイトのパラジウム化合物に対するモル比率が0.1〜４である請求項１又は２記載のモノアルキルグリセリルエーテルの製法。3. The molar ratio of the tertiary phosphine or phosphite to the palladium compound is 0.1 to 4 when the palladium compound and tertiary phosphine or phosphite coexist in the reaction system in the first step. Manufacturing method of monoalkyl glyceryl ether. 第一の工程において、パラジウム化合物又はパラジウム−第三級ホスフィン錯体若しくはパラジウム−ホスファイト錯体のグリセリン誘導体(1)に対するモル比率が0.0001〜0.01である請求項１〜３のいずれかに記載のモ ノアルキルグリセリルエーテルの製法。The monomer according to any one of claims 1 to 3, wherein in the first step, the molar ratio of the palladium compound, the palladium-tertiary phosphine complex or the palladium-phosphite complex to the glycerol derivative (1) is 0.0001 to 0.01. A process for producing alkyl glyceryl ethers. 第一の工程において、共役ジエンが1,3-ブタジエンである請求項１〜４のいずれかに記載のモノアルキルグリセリルエーテルの製法。The process for producing a monoalkyl glyceryl ether according to any one of claims 1 to 4, wherein the conjugated diene is 1,3-butadiene in the first step.
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