JP4271363B2 - Preparation of alkenyl polyether - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、乳化重合用反応性界面活性剤あるいはその中間体等として有用な末端不飽和アルケニルポリ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】
末端不飽和アルケニルポリエーテルは、乳化重合用反応性界面活性剤あるいはその中間体等として有用な化合物である。特表平３−５０３１６８には、アリルアルコールに、アルカリ触媒下、ブチレンオキシドとエチレンオキシドを付加して末端不飽和アルケニルポリエーテルを得る方法が開示されている。
【０００３】
また、Macromolecules，32巻，5967頁（1999年）には、乳化重合用反応性界面活性剤として３−メチル−３−ブテン−１−オールから１０−（３−メチル−３−ブテニル）オキシ−１−デカンスルホン酸ナトリウムを合成する方法が記載されている。しかしながら、該アルコールにアルキレンオキシド等のエポキシ化合物を反応させて乳化重合用反応性界面活性剤あるいはその中間体等として有用な、末端不飽和アルケニルポリエーテルを製造する方法は、これまで知られていなかった。
【０００４】
本発明の課題は、乳化重合用反応性界面活性剤あるいはその中間体等として有用な末端不飽和アルケニルポリエーテルを製造する方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明は、式（Ｉ）で表される不飽和アルコール（以下化合物（Ｉ）という）と炭素数２〜１８のアルキレンオキシドとを、ルイス酸触媒又は複合金属酸化物触媒を用いて反応させる、式(II)で表わされるアルケニルポリエーテル（以下化合物(II)という）の製法、並びにこの化合物(II)に、さらにエチレンオキシドを反応させる、式(III)で表わされるアルケニルポリエーテル（以下化合物(III)という）の製法を提供する。
【０００６】
【化３】
【０００７】
［式中、ｐは２〜１６の整数、ＡＯは炭素数２〜１８のオキシアルキレン基、ｍは１〜５０の数を示す。またｍ個の-(ＡＯ)-基は、同一でも異なっていてもよい。］
【０００８】
【化４】
【０００９】
［式中、ｐ，ＡＯ及びｍは前記と同じ意味を示し、ＥＯはオキシエチレン基、ｎは１〜１００の数を示す。〕
【００１０】
【発明の実施の形態】
式（Ｉ）において、ｐは２〜１６の整数であり、２〜９が好ましい。化合物（Ｉ）としては、３−メチル−３−ブテン−１−オール、４−メチル−４−ペンテン−１−オール、７−メチル−７−オクテン−１−オール等を挙げることができる。
【００１１】
式(II)及び(III)において、ＡＯは炭素数２〜１８のオキシアルキレン基であり、具体的には、オキシエチレン、オキシプロピレン、オキシブチレン、オキシジメチルエチレン、オキシデシルエチレン、オキシドデシルエチレン、オキシテトラデシルエチレン、オキシヘキサデシルエチレン等が挙げられる。
【００１２】
ｍはオキシアルキレン基の平均付加モル数を示す１〜５０の数で、好ましくは、１〜２０、特に好ましくは５〜２０の数であり、ｍ個の -(ＡＯ)-は、同一でも異なっていてもよい。(ＡＯ)mは、界面活性剤の疎水基を構成するので、ｍ個のオキシアルキレン基の半分以上は炭素数３以上のオキシアルキレン基であることが好ましく、特にすべてオキシブチレン基であることが好ましい。
【００１３】
式(III)において、ｎはオキシエチレン基の平均付加モル数を示す１〜１００の数で、好ましくは１〜５０の数である。
【００１４】
化合物（Ｉ）から化合物(II)を合成するときには、触媒としてルイス酸触媒又は複合金属酸化物触媒を用いる。反応触媒として水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、水素化ナトリウム等の塩基性触媒を用いると、二重結合の転移が起こり、乳化重合用反応性界面活性剤として用いた場合に共重合性に劣ることになる、内部に２重結合をもったアルケニルポリエーテルが、副生する。一方、反応触媒としてルイス酸又は複合金属酸化物を用いると、実質上、二重結合の異性化を生じさせずに反応させることができ、化合物(II)を高純度で得ることができる。
【００１５】
ルイス酸を触媒とする場合、使用できるルイス酸としては、塩化チタン、塩化第二鉄、四塩化スズ、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛、アルコキシチタン、臭化ホウ素、塩化ホウ素、三フッ化ホウ素、三フッ化ホウ素ジエチルエーテル錯体、塩化アルミニウム、臭化アルミニウム等が挙げられ、三フッ化ホウ素ジエチルエーテル錯体、四塩化スズが特に好ましい。ルイス酸の使用量は、生成する化合物(II)に対して０．１〜３重量％が適当である。反応温度は、０〜８０℃、好ましくは０〜５０℃、より好ましくは０〜３０℃である。反応時の圧力は常圧ないし加圧（好ましくは１ＭＰａ以下）である。
【００１６】
複合金属酸化物触媒としては、特開平７−２２７５４０、特開平１−１６４４３７等に記載のマグネシウムを含有する複合酸化物触媒が好ましく、マグネシウムと、Zn、Sb、Sn、Ti、Zr、Al、Ga、In、Tl、Co、Sc、La、Mnから選ばれる１種以上の金属とを複合させたものが挙げられる。特に好ましい複合金属酸化物はマグネシウム以外にZnとAlを含有する触媒である。複合金属酸化物触媒の使用量は、特に限定されないが、生成する化合物(II)に対して０．３〜３重量％が、適当である。反応温度は、８０〜１８０℃、好ましくは１００〜１５０℃、より好ましくは１１０〜１４０℃である。反応時の圧力は常圧ないし加圧（好ましくは１ＭＰａ以下）である。
【００１７】
化合物(II)にエチレンオキシドを反応させて化合物(III)を合成する場合には、触媒を含んだままの化合物(II)に、エチレンオキシドを導入し同一の触媒で続けて付加反応をおこなっても良いし、別の触媒を用いて反応させてもよい。触媒を変えるときには、化合物(II)の合成に用いた触媒は除去ないし失活させることが好ましい。化合物(II)から化合物(III)を合成するときには、塩基性触媒を使用することもできる。塩基性触媒の例としては水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド等のアルカリ金属の水酸化物やアルコキシド、水酸化バリウム等のアルカリ土類金属の水酸化物、テトラメチルアンモニウムヒドロキシド等の水酸化第４級アンモニウム塩等があげられる。特に水酸化カリウムが好ましい。塩基性触媒の使用量は、化合物(II)に対して０．５〜１０モル％が好ましく、１〜５モル％が更に好ましい。反応温度は８０〜１８０℃、好ましくは１００〜１５０℃、特に好ましくは１１０〜１３０℃である。
【００１８】
本発明の製造法によって得られるアルケニルポリエーテルは、高純度でラジカル重合性に富んでいる。化合物(III)はそれ自身反応性の非イオン界面活性剤として使用できる。さらに化合物(II)又は(III)の末端ＯＨ基を修飾してアニオン性の反応性界面活性剤を合成することができる。化合物(II)又は(III)に、たとえばスルファミン酸を反応させることにより、硫酸エステルアンモニウム塩を合成することができる。その他スルホン酸塩化、リン酸エステル塩化、カルボキシメチル化等の修飾反応を、特表平３−５０３１６８号第７頁に記載されている方法で行うことができる。
これらの反応性界面活性剤は、乳化重合の乳化剤やポリマーの改質剤として使用できる。
【００１９】
【実施例】
実施例１
攪拌機、温度計、滴下漏斗を備えた反応容器に３−メチル−３−ブテン−１−オール（東京化成（株）製）６０．０ｇ（０．６９７モル）を仕込み、窒素雰囲気下１０℃に冷却し、三フッ化ホウ素ジエチルエーテル錯体（和光純薬（株）製）１．９８ｇ（０．０１４０モル）を添加し、１，２−エポキシブタン（ブチレンオキシド）２５１ｇ（３．４８モル）を７〜１０℃で滴下し、滴下後、１０℃で、１時間熟成した。吸着剤キョワード５００ＳＨ（協和化学工業（株）製）６．２ｇを添加し、室温で１時間撹拌した後、減圧ろ過し、３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル付加体（以下アルケニルポリエーテルＡ-1という）を得た。得られたアルケニルポリエーテルＡ-1の1Ｈ−ＮＭＲスペクトルを図１に示す。
【００２０】
実施例２
実施例１において三フッ化ホウ素ジエチルエーテル錯体（和光純薬（株）製）を２．９７ｇ（０．０２０９モル）に、１，２−エポキシブタンを６０３ｇ（８．３６モル）にした以外は、実施例１と同様にして３−メチル−３−ブテン−１−オールの１，２−エポキシブタン１２モル付加体（以下アルケニルポリエーテルＡ-2という）を得た。
【００２１】
実施例３
実施例１において、三フッ化ホウ素ジエチルエーテル錯体を四塩化スズ（和光純薬（株）製）３．６３ｇ（０．０１３９モル）に変える以外は、実施例１と同様にして３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル付加体（以下アルケニルポリエーテルＡ-3という）を得た。
【００２２】
実施例４
攪拌機、温度計、滴下漏斗、還流管を備えた反応容器に３−メチル−３−ブテン−１−オール６０．０ｇ（０．６９７モル）、及び下記の方法に従って調製したＺｎ／Ａｌ／Ｍｇの複合金属酸化物触媒５．０ｇを仕込み、窒素雰囲気下１００〜１１０℃で１，２−エポキシブタン２５１ｇ（３．４８モル）を滴下した。滴下後、１１０℃で１時間熟成を行い室温まで冷却し、減圧ろ過して、３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル付加体（以下アルケニルポリエーテルＡ-4という）を得た。
【００２３】
＜複合金属酸化物触媒の製法＞
Ｚｎ（ＮＯ3）2・６Ｈ2Ｏ ５５．８ｇ、Ａｌ（ＮＯ3）3・９Ｈ2Ｏ１１２．５ｇ及びＭｇ（ＮＯ3）2・６Ｈ2Ｏ １４４．２ｇをイオン交換水１２９９ｇに溶解した溶液、０．２４ｍｏｌ／Ｌ Ｎａ2ＣＯ3水溶液、及び４ｍｏｌ／Ｌ ＮａＯＨ水溶液をそれぞれ１２．５ｍＬ／ｍｉｎ、９ｍＬ／ｍｉｎ、及び５〜７．５ｍＬ／ｍｉｎの液流量で５Ｌ容積の反応槽に同時供給した。反応槽には、予め水を５００ｇ入れておき、定速攪拌機で２５０ｒｐｍで撹拌した。反応槽は、液温度が１５±２℃になるように温度制御し、さらにｐＨが、９．７〜１０．３になるようにＮａＯＨ水溶液の添加量を調節し、２時間沈澱反応を行った後、各水溶液の供給を停止し、懸濁液を撹拌したまま１時間熟成させた。この懸濁液をろ過し、得られた白色固体をイオン交換水を用いて十分に洗浄した。洗浄後、１１０℃の温風乾燥器中で１２時間乾燥させ、式：[（Ｚｎ0.25Ｍｇ0.75）5/7Ａｌ2/7（ＯＨ）2]（ＣＯ3）1/7・ｃＨ2Ｏ］で表される白色固体状の触媒前駆体を得た。次いで、乾燥後の触媒前駆体を窒素気流中で５５０℃、２時間焼成し触媒を得た。
【００２４】
比較例１
攪拌機、温度計、蒸留管を備えた反応容器に３−メチル−３−ブテン−１−オール６６．０ｇ（０．７６６モル）、水酸化カリウム３．５２ｇ（０．０６２７モル）を仕込み、減圧下９０℃に加熱して水分及び該アルコール７．５ｇを留出させた。蒸留管を滴下漏斗と還流管に換え、窒素雰囲気下１００〜１１０℃で１，２−エポキシブタン２５１ｇ（３．４８モル）を滴下した。滴下後、１１０℃で３時間熟成を行い室温まで冷却し、減圧ろ過して、３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル付加体（以下アルケニルポリエーテルＡ-5という）を得た。得られたアルケニルポリエーテルＡ-5の1Ｈ−ＮＭＲスペクトルを図２に示す。
【００２５】
比較例２
オートクレーブに３−メチル−３−ブテン−１−オール３９０ｇ（４．５３モル）、粉末ナトリウムメトキシド７．３４ｇ（０．１３６モル）を仕込み、６５℃、０．００７ＭＰａで脱メタノール後、１４０℃、０．３ＭＰａの条件で１，２−エポキシブタン１６３１ｇ（２２．６モル）を注入し、３時間熟成を行い室温まで冷却し、減圧ろ過して、３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル付加体（以下アルケニルポリエーテルＡ-6という）を得た。
【００２６】
比較例３
オートクレーブに３−メチル−３−ブテン−１−オール３９０ｇ（４．５３モル）、KOH７．５８ｇ（０．１３５１モル）を仕込み、１４５℃、０．３ＭＰａの条件で１，２−エポキシブタン１６２１ｇ（２２．５モル）を付加して、３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル付加体（以下アルケニルポリエーテルＡ-7という）を得た。続いて１５０℃、０．３ＭＰａの条件でエチレンオキシ１９８５ｇ（４５．１モル）を付加して、３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル及びエチレンオキシド１０モル付加体（以下アルケニルポリエーテルＡ-8という）を得た。
【００２７】
実施例５
オートクレーブに実施例１で得られた３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル付加体５００ｇ（１．１２モル）、KOH１．８８ｇ（０．０３３６モル）を仕込み、１００℃、０．００４ＭＰａで脱水後、１２０℃、０．３ＭＰａの条件でエチレンオキシド４９３ｇ（１１．２モル）を付加して、３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル及びエチレンオキシド１０モル付加体（以下アルケニルポリエーテルＡ-9という）を得た。
【００２８】
実施例６
実施例５と同様にして３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル付加体５００ｇ（１．１２モル）にエチレンオキシド９８６ｇ（２２．４モル）を付加して、３−メチル−３−ブテン−１−オールの１，２−エポキシブタン５モル及びエチレンオキシド２０モル付加体（以下アルケニルポリエーテルＡ-10という）を得た。
【００２９】
実施例１〜６及び比較例１〜３で製造されたアルケニルポリエーテル中の３−メチル−２−ブテニルポリエーテルの含有率Ｉを下記の式により求めた。結果を表１に示す。
【００３０】
Ｉ（％）＝１００×ａ／（ａ＋ｂ）
（ここで、ａは、1Ｈ−ＮＭＲにより分析した３−メチル−２−ブテニル基の１位のメチレンプロトン（CDCl3、δ=4.0）の積分値であり、ｂは３−メチル−３−ブテニル基の２位のメチレンプロトン（CDCl3、δ=2.3）の積分値である。）
【００３１】
【表１】
【００３２】
【発明の効果】
本発明に従えば、乳化重合用反応性界面活性剤あるいはその中間体等として有用な末端不飽和アルケニルポリエーテルが製造できる。
【図面の簡単な説明】
【図１】 実施例１で得られたアルケニルポリエーテルＡ-1の1Ｈ−ＮＭＲスペクトルである。
【図２】 比較例１で得られたアルケニルポリエーテルＡ-5の1Ｈ−ＮＭＲスペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing a terminal unsaturated alkenyl polyether useful as a reactive surfactant for emulsion polymerization or an intermediate thereof.
[0002]
[Prior art and problems to be solved by the invention]
The terminal unsaturated alkenyl polyether is a useful compound as a reactive surfactant for emulsion polymerization or an intermediate thereof. JP-T-3-503168 discloses a method of obtaining terminally unsaturated alkenyl polyether by adding butylene oxide and ethylene oxide to allyl alcohol in the presence of an alkali catalyst.
[0003]
Also, Macromolecules, 32, 5967 (1999) describes 3-methyl-3-buten-1-ol to 10- (3-methyl-3-butenyl) oxy- as a reactive surfactant for emulsion polymerization. A method for synthesizing sodium 1-decanosulfonate is described. However, a method for producing a terminal unsaturated alkenyl polyether useful as an emulsion polymerization reactive surfactant or an intermediate thereof by reacting the alcohol with an epoxy compound such as alkylene oxide has not been known so far. It was.
[0004]
An object of the present invention is to provide a method for producing a terminal unsaturated alkenyl polyether useful as a reactive surfactant for emulsion polymerization or an intermediate thereof.
[0005]
[Means for Solving the Problems]
In the present invention, an unsaturated alcohol represented by formula (I) (hereinafter referred to as compound (I)) and an alkylene oxide having 2 to 18 carbon atoms are reacted using a Lewis acid catalyst or a composite metal oxide catalyst. A process for producing an alkenyl polyether represented by formula (II) (hereinafter referred to as compound (II)) and an alkenyl polyether represented by formula (III) (hereinafter referred to as compound (III), wherein this compound (II) is further reacted with ethylene oxide. ))).
[0006]
[Chemical 3]
[0007]
[Wherein, p represents an integer of 2 to 16, AO represents an oxyalkylene group having 2 to 18 carbon atoms, and m represents a number of 1 to 50. The m-(AO)-groups may be the same or different. ]
[0008]
[Formula 4]
[0009]
[Wherein, p, AO and m represent the same meaning as described above, EO represents an oxyethylene group, and n represents a number of 1 to 100. ]
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In formula (I), p is an integer of 2-16, and 2-9 are preferable. Examples of compound (I) include 3-methyl-3-buten-1-ol, 4-methyl-4-penten-1-ol, 7-methyl-7-octen-1-ol, and the like.
[0011]
In the formulas (II) and (III), AO is an oxyalkylene group having 2 to 18 carbon atoms, specifically, oxyethylene, oxypropylene, oxybutylene, oxydimethylethylene, oxydecylethylene, oxydecylethylene, Examples thereof include oxytetradecylethylene and oxyhexadecylethylene.
[0012]
m is a number of 1 to 50 indicating the average number of added moles of the oxyalkylene group, preferably 1 to 20, particularly preferably 5 to 20, and the m-(AO)-may be the same or different. It may be. (AO) m constitutes the hydrophobic group of the surfactant, so that more than half of the m oxyalkylene groups are preferably oxyalkylene groups having 3 or more carbon atoms, and in particular all oxybutylene groups. preferable.
[0013]
In the formula (III), n is a number of 1 to 100, preferably 1 to 50, indicating the average number of moles of oxyethylene group added.
[0014]
When synthesizing compound (II) from compound (I), a Lewis acid catalyst or a composite metal oxide catalyst is used as a catalyst. When a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, or sodium hydride is used as the reaction catalyst, double bond transfer occurs and copolymerization occurs when used as a reactive surfactant for emulsion polymerization. An alkenyl polyether having a double bond inside is produced as a by-product. On the other hand, when a Lewis acid or a composite metal oxide is used as a reaction catalyst, the reaction can be carried out substantially without causing double bond isomerization, and the compound (II) can be obtained with high purity.
[0015]
When a Lewis acid is used as a catalyst, usable Lewis acids include titanium chloride, ferric chloride, tin tetrachloride, zinc chloride, zinc bromide, zinc iodide, alkoxy titanium, boron bromide, boron chloride, trifluoride. Examples thereof include boron fluoride, boron trifluoride diethyl ether complex, aluminum chloride, aluminum bromide, and boron trifluoride diethyl ether complex and tin tetrachloride are particularly preferable. The amount of Lewis acid used is suitably from 0.1 to 3% by weight based on the resulting compound (II). The reaction temperature is 0 to 80 ° C, preferably 0 to 50 ° C, more preferably 0 to 30 ° C. The pressure during the reaction is normal pressure or pressurization (preferably 1 MPa or less).
[0016]
As the composite metal oxide catalyst, a composite oxide catalyst containing magnesium described in JP-A-7-227540, JP-A-1-164437 and the like is preferable. Magnesium, Zn, Sb, Sn, Ti, Zr, Al, Ga , In, Tl, Co, Sc, La, and Mn may be combined with one or more metals. A particularly preferable composite metal oxide is a catalyst containing Zn and Al in addition to magnesium. Although the usage-amount of a composite metal oxide catalyst is not specifically limited, 0.3-3 weight% is suitable with respect to the compound (II) to produce | generate. The reaction temperature is 80 to 180 ° C, preferably 100 to 150 ° C, more preferably 110 to 140 ° C. The pressure during the reaction is normal pressure or pressurization (preferably 1 MPa or less).
[0017]
When compound (III) is synthesized by reacting compound (II) with ethylene oxide, ethylene oxide may be introduced into compound (II) containing the catalyst and the addition reaction may be continued with the same catalyst. However, the reaction may be performed using another catalyst. When changing the catalyst, it is preferable to remove or deactivate the catalyst used in the synthesis of compound (II). When synthesizing compound (III) from compound (II), a basic catalyst can also be used. Examples of basic catalysts include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and sodium methoxide, alkoxides, hydroxides of alkaline earth metals such as barium hydroxide, and tetramethylammonium hydroxide. Examples thereof include quaternary ammonium hydroxide salts. In particular, potassium hydroxide is preferred. 0.5-10 mol% is preferable with respect to compound (II), and, as for the usage-amount of a basic catalyst, 1-5 mol% is still more preferable. The reaction temperature is 80 to 180 ° C, preferably 100 to 150 ° C, particularly preferably 110 to 130 ° C.
[0018]
The alkenyl polyether obtained by the production method of the present invention is highly pure and rich in radical polymerizability. Compound (III) can itself be used as a reactive nonionic surfactant. Furthermore, an anionic reactive surfactant can be synthesized by modifying the terminal OH group of compound (II) or (III). A sulfate ammonium salt can be synthesized by reacting compound (II) or (III) with, for example, sulfamic acid. Other modification reactions such as sulfonate formation, phosphate esterification, carboxymethylation and the like can be carried out by the methods described in JP-T-3-503168, page 7.
These reactive surfactants can be used as an emulsifier for emulsion polymerization or a modifier for polymers.
[0019]
【Example】
Example 1
A reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel was charged with 60.0 g (0.697 mol) of 3-methyl-3-buten-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and brought to 10 ° C. under a nitrogen atmosphere. After cooling, 1.98 g (0.0140 mol) of boron trifluoride diethyl ether complex (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 251 g (3.48 mol) of 1,2-epoxybutane (butylene oxide) was added. The solution was dropped at 7 to 10 ° C., and after the dropping, aging was performed at 10 ° C. for 1 hour. Adsorbent Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) (6.2 g) was added, stirred at room temperature for 1 hour, filtered under reduced pressure, and 1,2-epoxybutane of 3-methyl-3-buten-1-ol. A 5-mol adduct (hereinafter referred to as alkenyl polyether A-1) was obtained. The 1 H-NMR spectrum of the obtained alkenyl polyether A-1 is shown in FIG.
[0020]
Example 2
In Example 1, except that boron trifluoride diethyl ether complex (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 2.97 g (0.0209 mol) and 1,2-epoxybutane was changed to 603 g (8.36 mol). In the same manner as in Example 1, a 1,2-epoxybutane 12-mol adduct of 3-methyl-3-buten-1-ol (hereinafter referred to as alkenyl polyether A-2) was obtained.
[0021]
Example 3
In Example 1, except that the boron trifluoride diethyl ether complex was changed to 3.63 g (0.0139 mol) of tin tetrachloride (manufactured by Wako Pure Chemical Industries, Ltd.), 3-methyl- A 1,2-epoxybutane 5-mol adduct of 3-buten-1-ol (hereinafter referred to as alkenyl polyether A-3) was obtained.
[0022]
Example 4
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux tube, 60.0 g (0.697 mol) of 3-methyl-3-buten-1-ol, and Zn / Al / Mg prepared according to the following method A mixed metal oxide catalyst (5.0 g) was charged, and 251 g (3.48 mol) of 1,2-epoxybutane was added dropwise at 100 to 110 ° C. in a nitrogen atmosphere. After dropping, the mixture was aged at 110 ° C. for 1 hour, cooled to room temperature, filtered under reduced pressure, and 1,2-epoxybutane 5-mol adduct of 3-methyl-3-buten-1-ol (hereinafter referred to as alkenyl polyether A-). 4).
[0023]
<Production method of composite metal oxide catalyst>
A solution obtained by dissolving 55.8 g of Zn (NO 3 ) 2 .6H 2 O, 112.5 g of Al (NO 3 ) 3 .9H 2 O and 144.2 g of Mg (NO 3 ) 2 .6H 2 O in 1299 g of ion-exchanged water, A 0.24 mol / L Na 2 CO 3 aqueous solution and a 4 mol / L NaOH aqueous solution were simultaneously supplied to a 5 L reaction vessel at a liquid flow rate of 12.5 mL / min, 9 mL / min, and 5-7.5 mL / min, respectively. . In the reaction tank, 500 g of water was put in advance and stirred at 250 rpm with a constant speed stirrer. The temperature of the reaction vessel was controlled so that the liquid temperature became 15 ± 2 ° C., and the addition amount of the NaOH aqueous solution was adjusted so that the pH became 9.7 to 10.3, and the precipitation reaction was performed for 2 hours. Thereafter, the supply of each aqueous solution was stopped, and the suspension was aged for 1 hour with stirring. This suspension was filtered, and the resulting white solid was thoroughly washed with ion exchange water. After washing, it is dried in a hot air dryer at 110 ° C. for 12 hours, and the formula: [(Zn 0.25 Mg 0.75 ) 5/7 Al 2/7 (OH) 2 ] (CO 3 ) 1/7 · cH 2 O] A white solid catalyst precursor represented by the formula (1) was obtained. Next, the dried catalyst precursor was calcined at 550 ° C. for 2 hours in a nitrogen stream to obtain a catalyst.
[0024]
Comparative Example 1
A reaction vessel equipped with a stirrer, thermometer and distillation tube was charged with 66.0 g (0.766 mol) of 3-methyl-3-buten-1-ol and 3.52 g (0.0627 mol) of potassium hydroxide, and the pressure was reduced. The mixture was heated to 90 ° C. to distill water and 7.5 g of the alcohol. The distillation tube was replaced with a dropping funnel and a reflux tube, and 251 g (3.48 mol) of 1,2-epoxybutane was added dropwise at 100 to 110 ° C. in a nitrogen atmosphere. After dropping, the mixture was aged at 110 ° C. for 3 hours, cooled to room temperature, filtered under reduced pressure, and a 1,2-epoxybutane 5-mol adduct of 3-methyl-3-buten-1-ol (hereinafter referred to as alkenyl polyether A-). 5). The 1 H-NMR spectrum of the obtained alkenyl polyether A-5 is shown in FIG.
[0025]
Comparative Example 2
The autoclave was charged with 390 g (4.53 mol) of 3-methyl-3-buten-1-ol and 7.34 g (0.136 mol) of powdered sodium methoxide, and after methanol removal at 65 ° C. and 0.007 MPa, 140 ° C. Then, 1631 g (22.6 mol) of 1,2-epoxybutane was injected under the condition of 0.3 MPa, aged for 3 hours, cooled to room temperature, filtered under reduced pressure, and 3-methyl-3-buten-1-ol. 1,2-epoxybutane 5-mol adduct (hereinafter referred to as alkenyl polyether A-6) was obtained.
[0026]
Comparative Example 3
An autoclave was charged with 390 g (4.53 mol) of 3-methyl-3-buten-1-ol and 7.58 g (0.1351 mol) of KOH, and 1621 g of 1,2-epoxybutane under the conditions of 145 ° C. and 0.3 MPa ( 22.5 mol) was added to give a 1,2-epoxybutane 5-mol adduct of 3-methyl-3-buten-1-ol (hereinafter referred to as alkenyl polyether A-7). Subsequently, 1985 g (45.1 mol) of ethyleneoxy was added under conditions of 150 ° C. and 0.3 MPa, and 5 mol of 1,2-epoxybutane of 3-methyl-3-buten-1-ol and 10 mol of ethylene oxide were added. The product (hereinafter referred to as alkenyl polyether A-8) was obtained.
[0027]
Example 5
An autoclave was charged with 500 g (1.12 mol) of 1,2-epoxybutane 5-mol adduct of 3-methyl-3-buten-1-ol obtained in Example 1 and 1.88 g (0.0336 mol) of KOH. After dehydration at 100 ° C. and 0.004 MPa, 493 g (11.2 mol) of ethylene oxide was added under the conditions of 120 ° C. and 0.3 MPa to give 1,2-epoxy of 3-methyl-3-buten-1-ol. An adduct of 5 mol of butane and 10 mol of ethylene oxide (hereinafter referred to as alkenyl polyether A-9) was obtained.
[0028]
Example 6
In the same manner as in Example 5, 986 g (22.4 mol) of ethylene oxide was added to 500 g (1.12 mol) of 1,2-epoxybutane 5-mol adduct of 3-methyl-3-buten-1-ol, An adduct of 5 moles of 1,2-epoxybutane and 20 moles of ethylene oxide (hereinafter referred to as alkenyl polyether A-10) of 3-methyl-3-buten-1-ol was obtained.
[0029]
The content I of 3-methyl-2-butenyl polyether in the alkenyl polyether produced in Examples 1 to 6 and Comparative Examples 1 to 3 was determined by the following formula. The results are shown in Table 1.
[0030]
I (%) = 100 × a / (a + b)
(Where a is the integral value of the 1-position methylene proton (CDCl 3 , δ = 4.0) of the 3-methyl-2-butenyl group analyzed by 1 H-NMR, and b is 3-methyl-3- (This is the integral value of the 2-position methylene proton (CDCl 3 , δ = 2.3) of the butenyl group.)
[0031]
[Table 1]
[0032]
【The invention's effect】
According to the present invention, a terminal unsaturated alkenyl polyether useful as a reactive surfactant for emulsion polymerization or an intermediate thereof can be produced.
[Brief description of the drawings]
1 is a 1 H-NMR spectrum of alkenyl polyether A-1 obtained in Example 1. FIG.
2 is a 1 H-NMR spectrum of alkenyl polyether A-5 obtained in Comparative Example 1. FIG.
Claims (3)
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